Phase difference plate, circularly polarizing plate, and image display device

ABSTRACT

A phase difference plate including an optically anisotropic layer obtained by curing a composition (A) containing a polymerizable liquid crystal compound with reverse wavelength dispersion and a polymerizable monomer, wherein the polymerizable liquid crystal compound with reverse wavelength dispersion has a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in the molecule thereof; the main chain mesogen and the side chain mesogen are oriented in different directions, whereby a birefringence Δn of the optically anisotropic layer has reverse wavelength dispersion property; and retardations of a layer obtained by curing a composition (A0) in which the polymerizable monomer in the composition (A) is replaced by the polymerizable liquid crystal compound with reverse wavelength dispersion and retardations of the optically anisotropic layer satisfy specific relationship; and a circularly polarizing plate and a display device including the same.

FIELD

The present invention relates to a phase difference plate, a circularlypolarizing plate, and an image display device. In particular, thepresent invention relates to a phase difference plate, a circularlypolarizing plate, and an image display device whose reverse wavelengthdispersion property can be easily controlled.

BACKGROUND

A phase difference plate is widely used as a component of a displaydevice such as a liquid crystal display device. It is preferable that aphase difference plate used in a display device expresses a desiredphase difference of λ/4, λ/2, or the like in the entire wavelengthregion for displaying (usually visible region). In order to express sucha phase difference, it is necessary that the phase difference plate hasso-called reverse wavelength dispersion, i.e., wavelength dispersion inwhich anisotropy for light with a long wavelength is higher than thatfor light with a short wavelength. As a phase difference plateexhibiting reverse wavelength dispersion property, e.g., those describedin Patent Literatures 1 to 6 are known.

CITATION LIST Patent Literature

Patent Literature 1: Japanese Patent Application Laid-open No. Hei10-68816 A

Patent Literature 2: Japanese Patent Application Laid-open No. Hei10-90521 A

Patent Literature 3: Japanese Patent Application Laid-open No. Hei11-52131 A

Patent Literature 4: Japanese Patent Application Laid-Open No.2000-284126 A (corresponding foreign publication: U.S. Pat. No.6,400,433B1)

Patent Literature 5: Japanese Patent Application Laid-Open No. 2001-4837

Patent Literature 6: International publication WO 2000/026705(corresponding foreign publication: European Pat. ApplicationPublication No. 1045261A1 and U.S. Pat. No. 6,565,974B1)

SUMMARY Technical Problem

In order to improve performance of a display device, it is necessary toadjust reverse wavelength dispersion of a phase difference plate used inthe display device such that the reverse wavelength dispersion isslightly increased or decreased in accordance with the design of thedisplay device. However, in prior art, it is difficult to configure thephase difference plate so as to have desired reverse wavelengthdispersion property without impairing optical performance and mechanicalperformance.

Therefore, an object of the present invention is to provide a phasedifference plate that has reverse wavelength dispersion property thatcan be easily controlled with precision.

Another object of the present invention is to provide a display devicethat includes the phase difference plate that has reverse wavelengthdispersion property that can be easily controlled with precision, isinexpensive, and has good display performance due to the phasedifference plate, and a component thereof.

Solution to Problem

The present inventor has studied to solve the problems. As a result, theinventor has found that the problems can be solved when a compoundhaving specific mesogens in the molecule is used as a polymerizableliquid crystal compound with reverse wavelength dispersion and thecompound is oriented in combination with a polymerizable monomer to forman optically anisotropic layer having a certain optical property. Thus,the present invention has been accomplished.

Accordingly, the present invention provides as follows.

(1) A phase difference plate comprising an optically anisotropic layerobtained by curing a composition (A) containing a polymerizable liquidcrystal compound with reverse wavelength dispersion and a polymerizablemonomer, wherein:

the polymerizable liquid crystal compound with reverse wavelengthdispersion has a main chain mesogen and a side chain mesogen bonded tothe main chain mesogen in the molecule thereof;

-   -   the main chain mesogen and the side chain mesogen of the        polymerizable liquid crystal compound with reverse wavelength        dispersion are oriented in different directions in the optically        anisotropic layer, whereby a birefringence Δn of the optically        anisotropic layer has reverse wavelength dispersion property;        and

retardations Re0 (450 nm), Re0 (550 nm), and Re0 (650 nm) at wavelengthsof 450 nm, 550 nm, and 650 nm of a layer obtained by curing acomposition (A0) in which the polymerizable monomer in the composition(A) is replaced by the polymerizable liquid crystal compound withreverse wavelength dispersion and retardations Re (450 nm), Re (550 nm),and Re (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nm of theoptically anisotropic layer satisfy relationship of the followingexpressions (i) and (ii):Re0 (450 nm)/Re0 (550 nm)>Re (450 nm)/Re (550 nm)  Expression (i)Re0 (650 nm)/Re0 (550 nm)<Re (650 nm)/Re (550 nm)  Expression (ii).

(2) A phase difference plate comprising an optically anisotropic layerobtained by curing a composition (A) containing a polymerizable liquidcrystal compound with reverse wavelength dispersion and a polymerizablemonomer, wherein:

the polymerizable liquid crystal compound with reverse wavelengthdispersion has a main chain mesogen and a side chain mesogen bonded tothe main chain mesogen in the molecule thereof;

the main chain mesogen and the side chain mesogen of the polymerizableliquid crystal compound with reverse wavelength dispersion are orientedin different directions in the optically anisotropic layer, whereby abirefringence Δn of the optically anisotropic layer has reversewavelength dispersion property; and

retardations Re0 (450 nm), Re0 (550 nm), and Re0 (650 nm) at wavelengthsof 450 nm, 550 nm, and 650 nm of a layer obtained by curing acomposition (A0) in which the polymerizable monomer in the composition(A) was replaced by the polymerizable liquid crystal compound withreverse wavelength dispersion and retardations Re (450 nm), Re (550 nm),and Re (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nm of theoptically anisotropic layer satisfy relationship of the followingexpressions (iii) and (iv):Re0 (450 nm)/Re0 (550 nm)<Re (450 nm)/Re (550 nm)  Expression (iii)Re0 (650 nm)/Re0 (550 nm)>Re (650 nm)/Re (550 nm)  Expression (iv).(3) The phase difference plate according to (1) or (2), wherein

the polymerizable liquid crystal compound with reverse wavelengthdispersion is a compound represented by the following formula (I):

[in the formula, Y¹ to Y⁶ are each independently a chemical single bond,—O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—,wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbonatoms;

G¹ and G² are each independently a divalent aliphatic group having 1 to20 carbon atoms and optionally having a substituent [the aliphatic groupmay have one or more of —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—,—NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)— inserted thereinto per onealiphatic group, provided that a case where two or more —O— groups or—S— groups are adjacently inserted is excluded, wherein R² is a hydrogenatom or an alkyl group having 1 to 6 carbon atoms];

Z¹ and Z² are each independently an alkenyl group having 2 to 10 carbonatoms that may be substituted by a halogen atom;

A^(x) is an organic group of 2 to 30 carbon atoms having at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring; A^(y) is a hydrogenatom, an alkyl group having 1 to 12 carbon atoms and optionally having asubstituent, an alkenyl group having 2 to 12 carbon atoms and optionallyhaving a substituent, a cycloalkyl group having 3 to 12 carbon atoms andoptionally having a substituent, —C(═O)—R³, —SO₂—R⁶, or an organic groupof 2 to 30 carbon atoms having at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring and an aromaticheterocyclic ring, wherein the aromatic ring of A^(x) and A^(y) may havea substituent, and A^(x) and A^(y) may together form a ring, and whereinR³ is an alkyl group having 1 to 12 carbon atoms and optionally having asubstituent, an alkenyl group having 2 to 12 carbon atoms and optionallyhaving a substituent, and a cycloalkyl group having 3 to 12 carbon atomsand optionally having a substituent, and R⁶ is an alkyl group having 1to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, aphenyl group, or a 4-methylphenyl group;

A¹ is a trivalent aromatic group optionally having a substituent;

A² and A³ are each independently a divalent aromatic group having 6 to30 carbon atoms and optionally having a substituent; and

Q¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms andoptionally having a substituent].

(4) The phase difference plate according to (1) or (2), wherein thepolymerizable liquid crystal compound with reverse wavelength dispersionis a compound represented by the following formula (V):

[in the formula Y^(1w) to Y^(8w) are each independently a chemicalsingle bond, —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—,—C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or—NR¹—O—, wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6carbon atoms;

G^(1w) and G^(2w) are each independently a divalent linear aliphaticgroup having 1 to 20 carbon atoms and optionally having a substituent,wherein the linear aliphatic group may have one or more of —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR^(2w)—C(═O)—, —C(═O)—NR^(2w)—,—NR^(2w)—, or —C(═O)— inserted thereinto per one aliphatic group,provided that a case where two or more —O— groups or —S— groups areadjacently inserted is excluded, and wherein R^(2w) is a hydrogen atomor an alkyl group having 1 to 6 carbon atoms;

Z^(1w) and Z^(2w) are each independently an alkenyl group having 2 to 10carbon atoms that may be substituted by a halogen atom;

A^(xw) is an organic group of 2 to 30 carbon atoms having at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring;

A^(yw) is a hydrogen atom, an alkyl group having 1 to 20 carbon atomsand optionally having a substituent, an alkenyl group having 2 to 20carbon atoms and optionally having a substituent, an alkynyl grouphaving 2 to 20 carbon atoms and optionally having a substituent, acycloalkyl group having 3 to 12 carbon atoms and optionally having asubstituent, —C(═O)—R^(3w), —SO₂—R^(4w), —C(═S)NH—R^(9w), or an organicgroup of 2 to 30 carbon atoms having at least one aromatic ring selectedfrom the group consisting of an aromatic hydrocarbon ring and anaromatic heterocyclic ring, wherein R^(3w) is an alkyl group having 1 to20 carbon atoms and optionally having a substituent, an alkenyl grouphaving 2 to 20 carbon atoms and optionally having a substituent, acycloalkyl group having 3 to 12 carbon atoms and optionally having asubstituent, or an aromatic hydrocarbon group having 5 to 12 carbonatoms, R^(4w) is an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenylgroup, and R^(9w) is an alkyl group having 1 to 20 carbon atoms andoptionally having a substituent, an alkenyl group having 2 to 20 carbonatoms and optionally having a substituent, a cycloalkyl group having 3to 12 carbon atoms and optionally having a substituent, or an aromaticgroup having 5 to 20 carbon atoms and optionally having a substituent,wherein the aromatic ring of A^(xw) and A^(yw) may have a substituent,and A^(xw) and A^(yw) may together form a ring;

A^(1w) is a trivalent aromatic group optionally having a substituent;

A^(2w) and A^(3w) are each independently a divalent alicyclichydrocarbon group having 3 to 30 carbon atoms and optionally having asubstituent;

A^(4w) and A^(5w) are each independently a divalent aromatic grouphaving 6 to 30 carbon atoms and optionally having a substituent; and

Q^(1w) is a hydrogen atom or an alkyl group having 1 to 6 carbon atomsand optionally having a substituent].

(4.1) The aforementioned phase difference plate, wherein the totalnumber of π electrons included in the aforementioned A^(xw) and A^(yw)is 4 or more and 24 or less.

(4.2) The aforementioned phase difference plate, wherein theaforementioned A^(1w) is a trivalent benzene ring group or a trivalentnaphthalene ring group that may have a substituent.

(4.3) The aforementioned phase difference plate, wherein theaforementioned Y^(1w) to Y^(8w) are each independently a chemical singlebond, —O—, —O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.

(4.4) The aforementioned phase difference plate, wherein theaforementioned Z^(1w) and Z^(2w) are each independently CH₂═CH—,CH₂═C(CH₃)—, or CH₂═C(Cl)—.

(4.5) The aforementioned phase difference plate, wherein theaforementioned G^(1w) and G^(2w) are each independently a divalentaliphatic group having 1 to 20 carbon atoms and optionally having asubstituent (the aliphatic group may have one or more of —O—, —O—C(═O)—,—C(═O)—O—, or —C(═O)— inserted thereinto per one aliphatic group,provided that a case where two or more —O— groups are adjacentlyinserted is excluded).(4.6) The aforementioned phase difference plate, wherein theaforementioned G^(1w) and G^(2w) are each independently an alkylenegroup having 1 to 12 carbon atoms.(5) The phase difference plate according to (3), wherein thepolymerizable monomer is a non-liquid crystal compound represented bythe following formula (III):

(in the formula (III), Y^(1x) to Y^(6x), G^(1x), G^(2x), Z^(1x), Z^(2x),A^(xx), A^(yx), A^(1x) to A^(3x), and Q^(1x) have the same meanings asY¹ to Y⁶, G¹, G², Z¹, Z², A^(x), A^(y), A¹ to A³, and Q¹, respectively,in the formula (I), and at least one of them is different from thecorresponding group in the co-used compound (I)).(6) The phase difference plate according to any one of (1) to (5),wherein the polymerizable monomer has a mesogen, and the mesogen of thepolymerizable monomer is oriented in parallel to a main chain mesogen ofthe polymerizable liquid crystal compound with reverse wavelengthdispersion in the optically anisotropic layer.(7) The phase difference plate according to any one of (1) to (5),wherein the polymerizable monomer has a mesogen, and the mesogen of thepolymerizable monomer is oriented in parallel to a side chain mesogen ofthe polymerizable liquid crystal compound with reverse wavelengthdispersion in the optically anisotropic layer.(8) The phase difference plate according to any one of (1) to (7),wherein a ratio of the polymerizable monomer in the composition (A) is 1to 100 parts by weight relative to 100 parts by weight of thepolymerizable liquid crystal compound with reverse wavelengthdispersion.(9) A circularly polarizing plate comprising the phase difference plateaccording to any one of (1) to (8) and a linear polarizer.(10) The circularly polarizing plate according to (9), wherein a phasedifference of the phase difference plate at a wavelength of 550 nm is100 to 150 nm, and an angle between a slow axis of the phase differenceplate and a transmission axis of the linear polarizer is 45°.(11) An image display device comprising the phase difference plateaccording to any one of (1) to (8).

Advantageous Effects of Invention

The phase difference plate of the present invention has reversewavelength dispersion property that can be easily controlled withprecision. Therefore, the circularly polarizing plate of the presentinvention and the image display device of the present invention thatinclude the phase difference plate of the present invention can providea display device that is inexpensive and has favorable displayperformance and components thereof.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inComparative Example 1.

FIG. 2 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in ComparativeExample 1.

FIG. 3 is a graph showing a relationship between the azimuth angle ofpolarization and the measured absorption, which are measured inReference Example 1.

FIG. 4 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inExample 1, in comparison with Comparative Example 1.

FIG. 5 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in Example 1, incomparison with Comparative Example 1.

FIG. 6 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inExample 2, in comparison with Comparative Example 1.

FIG. 7 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in Example 2, incomparison with Comparative Example 1.

FIG. 8 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inExample 3, in comparison with Comparative Example 1.

FIG. 9 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in Example 3, incomparison with Comparative Example 1.

FIG. 10 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inExample 4, in comparison with Comparative Example 1.

FIG. 11 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in Example 4, incomparison with Comparative Example 1.

FIG. 12 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inExample 5, in comparison with Comparative Example 1.

FIG. 13 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in Example 5, incomparison with Comparative Example 1.

FIG. 14 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inComparative Example 2.

FIG. 15 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in ComparativeExample 2.

FIG. 16 is a graph showing wavelength dispersion property ofbirefringence Δn of a phase difference plate, which is measured inExample 6, in comparison with Comparative Example 2.

FIG. 17 is a graph showing wavelength dispersion property of refractiveindex of the phase difference plate, which is measured in Example 6, incomparison with Comparative Example 2.

DESCRIPTION OF EMBODIMENTS

The present invention will be described hereinbelow in detail withreference to illustrations and embodiments, but the present invention isnot limited to the following illustrations and embodiments and may beimplemented with any optional modifications without departing from thescope of the claims of the present invention and equivalents thereof.

Unless otherwise specified, “retardation” of an optically anisotropiclayer in a phase difference plate herein means a retardation Re in anin-plane direction. Retardation and birefringence Δn have a relationshipof Re=Δn×d (wherein d is the thickness of the optically anisotropiclayer).

[1. Phase Difference Plate]

The phase difference plate of the present invention has an opticallyanisotropic layer. The optically anisotropic layer is a layer obtainedby curing a composition (A) containing a polymerizable liquid crystalcompound with reverse wavelength dispersion and a polymerizable monomer.

[1.1. Polymerizable Liquid Crystal Compound with Reverse WavelengthDispersion]

In this application, a liquid crystal compound as a component of thecomposition (A) is a compound that is capable of exhibiting a liquidcrystal phase when the compound is mixed in the composition (A) andoriented. A polymerizable liquid crystal compound is a liquid crystalcompound polymerization of which in a state of the liquid crystal phasein the composition (A) can be performed, whereby the compound can form apolymer in which the orientation of molecules in the liquid crystalphase is maintained. Further, a polymerizable liquid crystal compoundwith reverse wavelength dispersion is a polymerizable liquid crystalcompound the resulting polymer of which when polymerized in such amanner shows reverse wavelength dispersion.

In this application, compounds having polymerizability (polymerizableliquid crystal compound, other compounds having polymerizability, etc.)as the component of the composition (A) are sometimes collectivelyreferred to as “polymerizable compound”.

In the present invention, the polymerizable liquid crystal compound withreverse wavelength dispersion has a main chain mesogen and a side chainmesogen bonded to the main chain mesogen in the molecule thereof. In astate where the polymerizable liquid crystal compound with reversewavelength dispersion is oriented, the side chain mesogen may beoriented in a direction different from that of the main chain mesogen.Therefore, the main chain mesogen and the side chain mesogen may beoriented in different directions in the optically anisotropic layer. Asa result of this orientation, the birefringence Δn of the opticallyanisotropic layer exhibits reverse wavelength dispersion property.

[1.2. Compound (I)]

Examples of the polymerizable liquid crystal compound with reversewavelength dispersion may include a compound represented by thefollowing formula (I) (this may be referred to hereinbelow as “compound(I)”).

When the polymerizable liquid crystal compound with reverse wavelengthdispersion is the compound (I), a —Y³-A²-Y¹-A¹-Y²-A³-Y⁴— group is themain chain mesogen, and a >A¹-C(Q¹)=N—N(A^(x))A^(y) group is the sidechain mesogen. The A¹ group affects nature of both the main chainmesogen and the side chain mesogen.

In the formula, Y¹ to Y⁶ are each independently a chemical single bond,—O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—.

Herein, R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbonatoms.

Examples of the alkyl group having 1 to 6 carbon atoms of R¹ may includea methyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group,and a n-hexyl group.

Herein, R¹ is preferably a hydrogen atom or an alkyl group having 1 to 4carbon atoms.

Among these, it is preferable that Y¹ to Y⁶ are each independently achemical single bond, —O—, —O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.

G¹ and G² are each independently a divalent aliphatic group having 1 to20 carbon atoms and optionally having a substituent.

Examples of the divalent aliphatic group having 1 to 20 carbon atoms mayinclude an aliphatic group having a linear structure; and an aliphaticgroup having an alicyclic structure such as a saturated cyclichydrocarbon (cycloalkane) structure and an unsaturated cyclichydrocarbon (cycloalkene) structure.

Examples of the substituent may include a halogen atom such as afluorine atom, a chlorine atom, a bromine atom, and an iodine atom; andan alkoxy group having 1 to 6 carbon atoms such as a methoxy group, anethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group,a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, and an-hexyloxy group. A fluorine atom, a methoxy group, and an ethoxy groupare preferable.

The aliphatic group may have one or more of —O—, —S—, —O—C(═O)—,—C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)—inserted thereinto per one aliphatic group (provided that a case wheretwo or more —O— groups or —S— groups are adjacently inserted isexcluded).

Among these, —O—, —O—C(═O)—, —C(═O)—O—, and —O—C(═O)—O— are preferable.

Herein, R² is a hydrogen atom or an alkyl group having 1 to 6 carbonatoms, like the aforementioned R¹. A hydrogen atom and a methyl groupare preferable.

Specific examples of the aliphatic group having these groups insertedthereinto may include —CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—S—CH₂—CH₂—,—CH₂—CH₂—O—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—C(═O)—O—CH₂—, —CH₂—O—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—NR²—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—NR²—CH₂—, —CH₂—NR²—CH₂—CH₂—,and —CH₂—C(═O)—CH₂—.

Among these, from the viewpoint of favorably expressing the desiredeffect of the present invention, it is preferable that G¹ and G² areeach independently an aliphatic group having a linear structure such asan alkylene group having 1 to 20 carbon atoms and an alkenylene grouphaving 2 to 20 carbon atoms. They each are more preferably an alkylenegroup having 1 to 12 carbon atoms such as a methylene group, an ethylenegroup, a trimethylene group, a propylene group, a tetramethylene group,a pentamethylene group, a hexamethylene group, and an octamethylenegroup, and particularly preferably a tetramethylene group [—(CH₂)₄—] anda hexamethylene group [—(CH₂)₆—]

Z¹ and Z² are each independently an alkenyl group having 2 to 10 carbonatoms that may be substituted by a halogen atom.

It is preferable that the number of carbon atoms in the alkenyl group is2 to 6. Examples of the halogen atom that is a substituent on thealkenyl group of Z¹ and Z² may include a fluorine atom, a chlorine atom,and a bromine atom. A chlorine atom is preferable.

Specific examples of the alkenyl group having 2 to 10 carbon atoms of Z¹and Z² may include CH₂═CH—, CH₂═C(CH₃)—, CH₂═CH—CH₂—, CH₃—CH═CH—,CH₂═CH—CH₂—CH₂—, CH₂═C(CH₃)—CH₂—CH₂—, (CH₃)₂C═CH—CH₂—,(CH₃)₂C═CH—CH₂—CH₂—, CH₂═C(Cl)—, CH₂═C(CH₃)—CH₂—, and CH₃—CH═CH—CH₂—.

Among these, from the viewpoint of favorably expressing the desiredeffect of the present invention, it is preferable that Z¹ and Z² areeach independently CH₂═CH—, CH₂═C(CH₃)—, CH₂═C(Cl)—, CH₂═CH—CH₂—,CH₂═C(CH₃)—CH₂—, or CH₂═C(CH₃)—CH₂—CH₂—. They each are more preferablyCH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—, and further more preferablyCH₂═CH—.

A^(x) is an organic group of 2 to 30 carbon atoms having at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring.

In the present invention, “aromatic ring” means a cyclic structurehaving aromaticity in the broad sense based on Huckel rule, i.e., acyclic conjugated structure having (4n+2) π electrons, and a structurethat exhibits aromaticity by the involvement of a lone electron pair ofheteroatom such as sulfur, oxygen, and nitrogen, typified by thiophene,furan, benzothiazole, and the like, in a π electron system.

The organic group of 2 to 30 carbon atoms having at least one aromaticring selected from the group consisting of an aromatic hydrocarbon ringand an aromatic heterocyclic ring, of A^(x), may have a plurality ofaromatic rings, and may have an aromatic hydrocarbon ring and anaromatic heterocyclic ring.

Examples of the aromatic hydrocarbon ring may include a benzene ring, anaphthalene ring, and an anthracene ring. Examples of the aromaticheterocyclic ring may include a monocyclic aromatic heterocyclic ringsuch as a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring,a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring,an imidazole ring, an oxazole ring, and a thiazole ring; and a condensedaromatic heterocyclic ring such as a benzothiazole ring, a benzoxazolering, a quinoline ring, a phthalazine ring, a benzimidazole ring, abenzopyrazole ring, a benzofuran ring, and a benzothiophene ring.

The aromatic ring of A^(x) may have a substituent. Examples of thesubstituent may include a halogen atom such as a fluorine atom and achlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atomssuch as a methyl group, an ethyl group, and a propyl group; an alkenylgroup having 2 to 6 carbon atoms such as a vinyl group and an allylgroup; a halogenated alkyl group having 1 to 6 carbon atoms such as atrifluoromethyl group; a substituted amino group such as a dimethylaminogroup; an alkoxy group having 1 to 6 carbon atoms such as a methoxygroup, an ethoxy group, and an isopropxy group; a nitro group; an arylgroup such as a phenyl group and a naphthyl group; —C(═O)—R⁴;—C(═O)—OR⁴; and —SO₂R⁴. Herein, R⁴ is an alkyl group having 1 to 6carbon atoms or an aryl group having 6 to 14 carbon atoms.

The aromatic ring of A^(x) may have a plurality of substituents that arethe same or different, and two adjacent substituents may be bondedtogether to form a ring. The formed ring may be a monocyclic ring or acondensed polycyclic ring.

The “number of carbon atoms” in the organic group having 2 to 30 carbonatoms of A^(x) means the total number of carbon atoms in the entireorganic group, although carbon atoms in the substituents are excludedtherefrom (the same applies to A^(y) which will be described later).

Examples of the organic group of 2 to 30 carbon atoms having at leastone aromatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring of A^(x) may includean aromatic hydrocarbon ring group; an aromatic heterocyclic ring group;an alkyl group of 3 to 30 carbon atoms having at least one aromatic ringselected from the group consisting of an aromatic hydrocarbon ring groupand an aromatic heterocyclic ring group; an alkenyl group of 4 to 30carbon atoms having at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring group and an aromaticheterocyclic ring group; and an alkynyl group of 4 to 30 carbon atomshaving at least one aromatic ring selected from the group consisting ofan aromatic hydrocarbon ring group and an aromatic heterocyclic ringgroup.

A^(y) is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms andoptionally having a substituent, an alkenyl group having 2 to 12 carbonatoms and optionally having a substituent, a cycloalkyl group having 3to 12 carbon atoms and optionally having a substituent, —C(═O)—R³,—SO₂—R⁶, or an organic group of 2 to 30 carbon atoms having at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring.

Examples of an alkyl group having 1 to 12 carbon atoms in the alkylgroup having 1 to 12 carbon atoms and optionally having a substituent ofA^(y) may include a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group,a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, an-nonyl group, and a n-decyl group.

Examples of a substituent in the alkyl group having 1 to 12 carbon atomsand optionally having a substituent of A^(y) may include a halogen atomsuch as a fluorine atom and a chlorine atom; a cyano group; asubstituted amino group such as a dimethylamino group; an alkoxy grouphaving 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, andan isopropoxy group; a nitro group; an aryl group such as a phenyl groupand a naphthyl group; a cycloalkyl group having 3 to 8 carbon atoms suchas a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group;—C(═O)—R⁴; —C(═O)—OR⁴; and —SO₂R⁴. Herein, R⁴ has the same meanings asdescribed above.

Examples of an alkenyl group having 2 to 12 carbon atoms in the alkenylgroup having 2 to 12 carbon atoms and optionally having a substituent ofA^(y) may include a vinyl group, a propenyl group, an isopropenyl group,a butenyl group, and a pentenyl group.

Examples of a cycloalkyl group having 3 to 12 carbon atoms in thecycloalkyl group having 3 to 12 carbon atoms and optionally having asubstituent of A^(y) may include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of substituents in the alkenyl group having 2 to 12 carbonatoms and optionally having a substituent and the cycloalkyl grouphaving 3 to 12 carbon atoms and optionally having a substituent of A^(y)may include a halogen atom such as a fluorine atom and a chlorine atom;a cyano group; a substituted amino group such as a dimethylamino group;an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, anethoxy group, and an isopropoxy group; a nitro group; an aryl group suchas a phenyl group and a naphthyl group; a cycloalkyl group having 3 to 8carbon atoms such as a cyclopropyl group, a cyclopentyl group, and acyclohexyl group; —C(═O)—R⁴; —C(═O)—OR⁴; and —SO₂R⁴. Herein, R⁴ has thesame meanings as described above.

In the group represented by —C(═O)—R³ of A^(y), R³ is an alkyl grouphaving 1 to 12 carbon atoms and optionally having a substituent, analkenyl group having 2 to 12 carbon atoms and optionally having asubstituent, or a cycloalkyl group having 3 to 12 carbon atoms andoptionally having a substituent. Specific examples thereof may includethose exemplified as the examples of the alkyl group having 1 to 12carbon atoms and optionally having a substituent, the alkenyl grouphaving 2 to 12 carbon atoms and optionally having a substituent, and thecycloalkyl group having 3 to 12 carbon atoms and optionally having asubstituent of the aforementioned A^(y).

In the group represented by —SO₂—R⁶ of A^(y), R⁶ is an alkyl grouphaving 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbonatoms, a phenyl group, or a 4-methylphenyl group.

Specific examples of the alkyl group having 1 to 12 carbon atoms and thealkenyl group having 2 to 12 carbon atoms of R⁶ may include thoseexemplified as the examples of the alkyl group having 1 to 12 carbonatoms and the alkenyl group having 2 to 12 carbon atoms of theaforementioned A^(y).

The aromatic ring of the aforementioned A^(x) and A^(y) may have asubstituent. The aforementioned A^(x) and A^(y) may together form aring.

Examples of the organic group of 2 to 30 carbon atoms having at leastone aromatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring of A^(y) may includethose exemplified as the examples regarding the aforementioned A^(x).

The aromatic ring of A^(y) may have a substituent on any position.Examples of the substituent may include those exemplified as theexamples of the substituent on the aromatic ring of the aforementionedA^(x).

Specific examples of the aromatic ring of A^(x) and A^(y) are asfollows. However, in the present invention, the aromatic ring of A^(x)and A^(y) is not limited to the following examples. In the followingcompounds, [—] represents an atomic bond of the aromatic ring (the sameapplies to the following).

In the formulae, E is NR⁵, an oxygen atom, or a sulfur atom. Herein, R⁵is a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such asa methyl group and an ethyl group.

In the formulae, X, Y, and Z are each independently NR⁵, an oxygen atom,a sulfur atom, —SO—, or —SO₂— (provided that a case where oxygen atoms,sulfur atoms, —SO— groups, or —SO₂— groups are adjacent is excluded). R⁵has the same meanings as described above.

Among the aforementioned aromatic rings, the aromatic ring of A^(x) andA^(y) is preferably as follows.

The aromatic ring of A^(x) and A^(y) is particularly preferably asfollows.

A^(x) and A^(y) may together form a ring. In particular, it ispreferable that A^(x) and A^(y) form an unsaturated heterocyclic ringhaving 4 to 30 carbon atoms or an unsaturated carbon ring having 6 to 30carbon atoms, wherein these rings may optionally have a substituent.

The unsaturated heterocyclic ring having 4 to 30 carbon atoms and theunsaturated carbon ring having 6 to 30 carbon atoms are not particularlyrestricted, and may or may not have aromaticity. Examples thereof mayinclude rings shown in the following. The rings shown in the followingare a moiety represented by:

in the formula (I).

In the formulae, X, Y, and Z have the same meanings as described above.

The rings may have a substituent.

Examples of the substituent may include a halogen atom, a cyano group,an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6carbon atoms, a nitro group, —C(═O)—R⁴, —C(═O)—OR⁴, and —SO₂R⁴. Herein,R⁴ has the same meanings as described above.

The total number of n electrons included in A^(x) and A^(y) ispreferably 4 or more and 24 or less, and more preferably 6 or more and18 or less from the viewpoint of favorably expressing the desired effectof the present invention.

Examples of preferred combination of A^(x) and A^(y) may include acombination of an aromatic group having 4 to 30 carbon atoms as A^(x)and a hydrogen atom or an alkyl group optionally having a substituent asA^(y), and a combination in which A^(x) and A^(y) together form anunsaturated heterocyclic ring or an unsaturated carbon ring. Preferredexamples of a substituent in the alkyl group optionally having asubstituent may include a cycloalkyl group, a cyano group, and a halogenatom such as a fluorine atom.

The combination is preferably a combination of the following structureas A^(x) and a hydrogen atom or an alkyl group optionally having asubstituent as A^(y).

The combination is particularly preferably a combination of thefollowing structure as A^(x) and a hydrogen atom or an alkyl groupoptionally having a substituent as A^(y). In the combination, apreferred substituent in the alkyl group optionally having a substituentis a cycloalkyl group, a cyano group, or a halogen atom such as afluorine atom. In the formulae, X and Y have the same meanings asdescribed above.

A¹ is a trivalent aromatic group optionally having a substituent. Thetrivalent aromatic group may be a trivalent carbocyclic aromatic groupor a trivalent heterocyclic aromatic group. From the viewpoint offavorably expressing the desired effect of the present invention, thetrivalent carbocyclic aromatic group is preferable, and a trivalentbenzene ring group and a trivalent naphthalene ring group represented bythe following formulae are more preferable. In the following formulae,substituents Y¹ and Y² are shown for the sake of convenience to clearlyshow a bonding state (Y¹ and Y² have the same meanings as describedabove, and the same applies to the following).

In particular, it is preferable that A¹ is a group represented by eachof the formulae (A11) to (A22), and more preferably a group representedby the formula (A11).

Examples of a substituent that may be included in the trivalent aromaticgroup of A¹ may include those exemplified as the examples of thesubstituent on the aromatic group of the aforementioned A^(x). It ispreferable that A¹ is a trivalent aromatic group having no substituent.

A² and A³ are each independently a divalent aromatic group having 6 to30 carbon atoms and optionally having a substituent.

The aromatic group of A² and A³ may be monocyclic or polycyclic.

Specific examples of A² and A³ may include the following groups.

The organic groups enumerated as the specific examples of theaforementioned A² and A³ may have a substituent on any position.Examples of the substituent may include a halogen atom, a cyano group, ahydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxygroup having 1 to 6 carbon atoms, a nitro group, and a —C(═O)—OR group.Herein, R is an alkyl group having 1 to 6 carbon atoms. Among these, ahalogen atom, an alkyl group, and alkoxy group are preferable. As thehalogen atom, a fluorine atom is more preferable. As the alkyl group, amethyl group, an ethyl group, and a propyl group are more preferable. Asthe alkoxy group, a methoxy group and an ethoxy group are morepreferable.

Among these, it is preferable that A² and A³ are each independently agroup represented by the following formulae (A23) and (A24) that mayoptionally have a substituent from the viewpoint of favorably expressingthe desired effect of the present invention, and the group representedby the formula (A23) and optionally having a substituent is morepreferable.

Q¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms andoptionally having a substituent.

Examples of the alkyl group having 1 to 6 carbon atoms and optionallyhaving a substituent may include those exemplified as the examplesregarding the aforementioned A^(x).

Among these, Q¹ is preferably a hydrogen atom or an alkyl group having 1to 6 carbon atoms, and more preferably a hydrogen atom or a methylgroup.

Specific examples of the compound (I) may include compounds representedby the following formulae (I)-1 to (I)-3.

All the compound represented by the formula (I) is not limited to acompound that is capable of exhibiting a liquid crystal phase. However,whether or not the compound is capable of exhibiting a liquid crystalphase can be easily determined by, e.g., preparing a composition (A) andactually orienting the composition.

[1.3. Method for Producing Compound (I)]

The compound (I) may be produced by, e.g., the following reaction.

(wherein Y¹ to Y⁶, G¹, G², Z¹, Z², A^(x), A^(y), A¹ to A³, and Q¹ havethe same meanings as described above.) Specifically, a hydrazinecompound represented by the formula (3) (hydrazine compound (3)) may bereacted with a carbonyl compound represented by the formula (4)(carbonyl compound (4)) at a molar ratio of [hydrazine compound (3)carbonyl compound (4)] of 1:2 to 2:1, and preferably 1:1.5 to 1.5:1 tohighly selectively produce a target compound represented by the formula(I) in high yield.

In this case, an acid catalyst, such as an organic acid such as(±)-10-camphorsulfonic acid and p-toluene sulfonic acid; and aninorganic acid such as hydrochloric acid and sulfuric acid, may be addedto perform the reaction. The addition of the acid catalyst may shortenthe reaction time and may improve the yield. The amount of the acidcatalyst to be added is usually 0.001 to 1 mol relative to 1 mol of thecarbonyl compound (4). The acid catalyst may be added as it is, or as asolution form in which the acid catalyst is dissolved in an appropriatesolution.

The solvent used in the reaction is not particularly limited so long asit is inert to the reaction. Examples of the solvent may include analcohol solvent such as methyl alcohol, ethyl alcohol, n-propyl alcohol,isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,tert-butyl alcohol, n-pentyl alcohol, and amyl alcohol; an ether solventsuch as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane,1,4-dioxane, and cyclopentyl methyl ether; an ester solvent such asethyl acetate, propyl acetate, and methyl propionate; an aromatichydrocarbon-based solvent such as benzene, toluene, and xylene; analiphatic hydrocarbon-based solvent such as n-pentane, n-hexane, andn-heptane; an amide-based solvent such as N,N-dimethylformamide,N-methylpyrrolidone, and triamide hexamethylphosphate; asulfur-containing solvent such as dimethyl sulfoxide and sulfolane; anda mixed solvent of two or more types thereof.

Among these, the alcohol solvent, the ether solvent, and a mixed solventof the alcohol solvent and the ether solvent are preferable.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 100 g relative to1 g of the hydrazine compound (3).

The reaction smoothly proceeds in a temperature range of −10° C. to theboiling point of the solvent to be used. The reaction time of eachreaction may vary depending on the reaction scale, and is usuallyseveral minutes to several hours.

The hydrazine compound (3) may be produced as follows.

(wherein A^(x) and A^(y) have the same meanings as described above. X isa leaving group such as a halogen atom, a methanesulfonyloxy group, anda p-toluenesulfonyloxy group.)

Specifically, a compound represented by the formula (2a) may be reactedwith hydrazine (1) in an appropriate solvent at a molar ratio of(compound (2a) hydrazine (1)) of 1:1 to 1:20, and preferably 1:2 to1:10, to obtain a corresponding hydrazine compound (3a). Further, thehydrazine compound (3a) may be reacted with a compound represented bythe formula (2b) to obtain the hydrazine compound (3).

As hydrazine (1), hydrazine monohydrate is usually used. As hydrazine(1), a commercially available product may be used as it is.

The solvent used in the reaction is not particularly limited so long asit is inert to the reaction. Examples of the solvent may include analcohol solvent such as methyl alcohol, ethyl alcohol, n-propyl alcohol,isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,tert-butyl alcohol, n-pentyl alcohol, and amyl alcohol; an ether solventsuch as diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane,1,4-dioxane, and cyclopentyl methyl ether; an aromatic hydrocarbon-basedsolvent such as benzene, toluene, and xylene; an aliphatichydrocarbon-based solvent such as n-pentane, n-hexane, and n-heptane; anamide-based solvent such as N,N-dimethylformamide, N-methylpyrrolidone,and triamide hexamethylphosphate; a sulfur-containing solvent such asdimethyl sulfoxide and sulfolane; and a mixed solvent of two or moretypes thereof.

Among these, the alcohol solvent, the ether solvent, and a mixed solventof the alcohol solvent and the ether solvent are preferable.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 100 g relative to1 g of hydrazine.

The reaction smoothly proceeds in a temperature range of −10° C. to theboiling point of the solvent to be used. The reaction time of eachreaction may vary depending on the reaction scale, and is usuallyseveral minutes to several hours.

The hydrazine compound (3) may also be produced by reducing a diazoniumsalt (5) through a publicly known method, as described in the following.

In the formula (5), A^(x) and A^(y) have the same meanings as describedabove. X⁻ is an anion that is a counter ion of diazonium. Examples of X⁻may include an inorganic anion such as a hexafluorophosphate ion, afluoroborate ion, a chloride ion, and a sulfate ion; and an organicanion such as a polyfluoroalkyl carboxylate ion, a polyfluoroalkylsulfonate ion, a tetraphenyl borate ion, an aromatic carboxylate ion,and an aromatic sulfonate ion.

Examples of the reducing agent used in the reaction may include a metalsalt reducing agent.

The metal salt reducing agent is generally a compound containinglow-valent metal or a compound having a metal ion and a hydride source(see “Yuki Gosei Jikkenhou Handbook (Organic synthesis experimentalmethod handbook)”, 1990, edited by The Society of Synthetic OrganicChemistry, Japan, published by Maruzen Co., Ltd., p. 810).

Examples of the metal salt reducing agent may include NaAlH₄,NaAlH_(n)(OR)_(m), LiAlH₄, iBu₂AlH, LiBH₄, NaBH₄, SnCl₂, CrCl₂, andTiCl₃.

In the reduction reaction, a known reaction condition may be adopted.For example, the reaction may be carried out under a condition describedin Publications such as Japanese Patent Application Laid-Open No.2005-336103 A, “Shin Jikken Kagaku Koza (New course of experimentalchemistry)”, 1978, published by Maruzen Co., Ltd., vol. 14, and “JikkenKagaku Koza (Course of experimental chemistry)”, 1992, published byMaruzen Co., Ltd., vol. 20.

The diazonium salt (5) may be produced from a compound such as anilineby a conventional method.

The carbonyl compound (4) may be typically produced by appropriatelybonding and modifying a plurality of known compounds having a desiredstructure through any combination of reactions of forming an etherlinkage (—O—), an ester linkage (—C(═O)—O— and —O—C(═O)—), a carbonatelinkage (—O—C(═O)—O—), and an amide linkage (—C(═O)NH— and —NHC(═O)—).

An ether linkage may be formed, e.g., as follows.

(i) A compound represented by the formula: D1-hal (hal represents ahalogen atom, and the same applies to the following) and a compoundrepresented by a formula: D2-OMet (Met represents an alkaline metal(mainly sodium), and the same applies to the following) are mixed andcondensed (Williamson synthesis). In the formulae, D1 and D2 areoptional organic groups (the same applies to the following).

(ii) A compound represented by the formula: D1-hal and a compoundrepresented by the formula: D2-OH are mixed in the presence of a basesuch as sodium hydroxide or potassium hydroxide and condensed.

(iii) A compound represented by the formula: D1-J (J represents an epoxygroup) and a compound represented by the formula: D2-OH are mixed in thepresence of a base such as sodium hydroxide or potassium hydroxide andcondensed.

(iv) A compound represented by the formula: D1-OFN (OFN represents agroup having an unsaturated bond) and a compound represented by theformula: D2-OMet are mixed in the presence of a base such as sodiumhydroxide or potassium hydroxide and subjected to an addition reaction.

(v) A compound represented by the formula: D1-hal and a compoundrepresented by the formula: D2-OMet are mixed in the presence of copperor cuprous chloride and condensed (Ullmann condensation).

An ester linkage and an amide linkage may be formed, e.g., as follows.

(vi) A compound represented by the formula: D1-COOH and a compoundrepresented by the formula: D2-OH or D2-NH₂ are subjected to dehydrationcondensation in the presence of a dehydration condensation agent(N,N-dicyclohexylcarbodiimide, etc.).

(vii) A compound represented by the formula: D1-COOH is reacted with ahalogenating agent to obtain a compound represented by the formula:D1-CO-hal, and the compound is reacted with a compound represented bythe formula: D2-OH or D2-NH₂ in the presence of a base.

(viii) A compound represented by the formula: D1-COOH is reacted with anacid anhydride to obtain a mixed acid anhydride, and the mixed acidanhydride is reacted with a compound represented by the formula: D2-OHor D2-NH₂.

(ix) A compound represented by the formula: D1-COOH and a compoundrepresented by the formula: D2-OH or D2-NH₂ are subjected to dehydrationcondensation in the presence of an acid catalyst or a base catalyst.

More specifically, among the carbonyl compound (4), a compound (4′) inwhich a group represented by the formula: Z²—Y⁶-G²-Y⁴-A³-Y²— in theformula (4) is the same as a group represented by the formula:Z¹—Y⁵-G¹-Y³-A²-Y¹—, and Y¹ is a group represented by Y¹¹—C(═O)—O— may beproduced by the following reaction.

(wherein Y³, Y⁵, G¹, Z¹, A¹, A², and Q¹ have the same meanings asdescribed above. Y¹¹ is a group having a structure such thatY¹¹—C(═O)—O— corresponds to Y¹. Y¹ has the same meanings as describedabove. L is a leaving group such as a hydroxyl group, a halogen atom, amethanesulfonyloxy group, or a p-toluenesulfonyloxy group.)

In the reaction, a dihydroxy compound represented by the formula (6)(compound (6)) may be reacted with a compound represented by the formula(7) (compound (7)) at a molar ratio of (compound (6):compound (7)) of1:2 to 1:4, and preferably 1:2 to 1:3 to highly selectively produce atarget compound (4′) in high yield.

When the compound (7) is a compound in which L in the formula (7) is ahydroxyl group (carboxylic acid), the reaction may be carried out in thepresence of a dehydration condensation agent such as1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride ordicyclohexyl carbodiimide to obtain a target compound.

The amount of the dehydration condensation agent to be used is usually 1to 3 mol relative to 1 mol of the compound (7).

When the compound (7) is a compound in which L in the formula (7) is ahalogen atom (acid halide), the reaction may be carried out in thepresence of a base to obtain a target compound.

Examples of the base for use may include an organic base such astriethylamine and pyridine; and an inorganic base such as sodiumhydroxide, sodium carbonate, and sodium hydrogen carbonate.

The amount of the base to be used is usually 1 to 3 mol relative to 1mol of the compound (7).

A case where the compound (7) is a compound in which L in the formula(7) is a methanesulfonyloxy group or a p-toluenesulfonyloxy group (mixedacid anhydride) is also the same as in the case in which L is a halogenatom.

Examples of the solvent used in the reaction may include a chlorinatedsolvent such as chloroform and methylene chloride; an amide-basedsolvent such as N-methylpyrrolidone, N,N-dimethyl formamide,N,N-dimethyl acetamide, and triamide hexamethylphosphate; an ether suchas 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,tetrahydropyran, and 1,3-dioxolan; a sulfur-containing solvent such asdimethyl sulfoxide and sulfolane; an aromatic hydrocarbon-based solventsuch as benzene, toluene, and xylene; an aliphatic hydrocarbon-basedsolvent such as n-pentane, n-hexane, and n-octane; an alicyclichydrocarbon-based solvent such as cyclopentane and cyclohexane; and amixed solvent of two or more types thereof.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 50 g relative to1 g of the hydroxy compound (6).

Many of the compounds (7) are known compounds, and may be produced byappropriately bonding and modifying a plurality of known compoundshaving a desired structure through any combination of reactions offorming an ether linkage (—O—), an ester linkage (—C(═O)—O— and—O—C(═O)—), a carbonate linkage (—O—C(═O)—O—), and an amide linkage(—C(═O)NH— and —NHC(═O)—).

In any of the reactions, a usual post-treatment operation in organicsynthesis chemistry may be carried out after completion of thereactions, and if desired, a known separation and purification operationsuch as column chromatography, recrystallization, and distillation maybe carried out to isolate a target compound.

The structure of the target compound may be identified by, e.g.,measurements such as NMR spectrometry, IR spectrometry, and massspectrometry, as well as elemental analysis.

[1.4. Compound (V)]

Other examples of the polymerizable liquid crystal compound with reversewavelength dispersion may include a compound represented by thefollowing formula (V) (this may be referred to hereinbelow as “compound(V)”).

When the polymerizable liquid crystal compound with reverse wavelengthdispersion is the compound (V), a—Y^(5w)-A^(4w)-Y^(3w)-A^(2w)-Y^(1w)-A^(1w)-Y^(2w)-A^(3w)-Y^(4w)-A^(5w)-Y^(6w)—group is the main chain mesogen, and a>A^(1w)-C(Q^(1w))=N—N(A^(xw))A^(yw) group is the side chain mesogen. TheA^(1w) group affects nature of both the main chain mesogen and the sidechain mesogen.

In the formula, Y^(1w) to Y^(8w) are each independently a chemicalsingle bond, —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—,—C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or—NR¹—O—.

Herein, definition of R¹ and preferred examples of Y^(1w) to Y^(8w) arethe same as those described regarding Y¹ to Y⁶ of the formula (I).

G^(1w) and G^(2w) are each independently a divalent aliphatic grouphaving 1 to 20 carbon atoms and optionally having a substituent.

Examples of the divalent aliphatic group having 1 to 20 carbon atoms mayinclude a divalent aliphatic group having a linear structure such as analkylene group having 1 to 20 carbon atoms and an alkenylene grouphaving 2 to 20 carbon atoms; and a divalent aliphatic group such as acycloalkanediyl group having 3 to 20 carbon atoms, a cycloalkenediylgroup having 4 to 20 carbon atoms, and a divalent alicyclic condensedring group having 10 to 30 carbon atoms.

Examples of the substituent on the divalent aliphatic group of G^(1w)and G^(2w) may include a halogen atom such as a fluorine atom, achlorine atom, a bromine atom, and an iodine atom; and an alkoxy grouphaving 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxygroup, a tert-butoxy group, a n-pentyloxy group, and a n-hexyloxy group.Among these, a fluorine atom, a methoxy group, and an ethoxy group arepreferable.

The aliphatic group may have one or more of —O—, —S—, —O—C(═O)—,—C(═O)—O—, —O—C(═O)—O—, —NR^(2w)—C(═O)—, —C(═O)—NR^(2w)—, —NR^(2w)—, or—C(═O)— inserted thereinto per one aliphatic group, provided that a casewhere two or more —O— groups or —S— groups are adjacently inserted isexcluded. Herein, R^(2w) is a hydrogen atom or an alkyl group having 1to 6 carbon atoms, like R¹, and preferably a hydrogen atom or a methylgroup.

It is preferable that the group inserted into the aliphatic group is—O—, —O—C(═O)—, —C(═O)—O—, or —C(═O)—.

Specific examples of the aliphatic group having these groups insertedthereinto may include —CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—S—CH₂—CH₂—,—CH₂—CH₂—O—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—C(═O)—O—CH₂—, —CH₂—O—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—NR²—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—NR²—CH₂—, —CH₂—NR²—CH₂—CH₂—,and —CH₂—C(═O)—CH₂—.

Among these, from the viewpoint of favorably expressing the desiredeffect of the present invention, it is preferable that G^(1w) and G^(2w)are each independently a divalent aliphatic group having a linearstructure such as an alkylene group having 1 to 20 carbon atoms and analkenylene group having 2 to 20 carbon atoms, more preferably analkylene group having 1 to 12 carbon atoms such as a methylene group, anethylene group, a trimethylene group, a propylene group, atetramethylene group, a pentamethylene group, a hexamethylene group, anoctamethylene group, and a decamethylene group [—(CH₂)₁₀—], andparticularly preferably a tetramethylene group [—(CH₂)₄—], ahexamethylene group [—(CH₂)₆—], an octamethylene group [—(CH₂)₈—], or adecamethylene group [—(CH₂)₁₀—].

Z^(1w) and Z^(2w) are each independently an alkenyl group having 2 to 10carbon atoms that is unsubstituted or substituted by a halogen atom.

Preferable examples of Z^(1w) and Z^(2w) are the same as those describedregarding Z¹ to Z² in the formula (I).

A^(xw) is an organic group of 2 to 30 carbon atoms having at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring.

The organic group of 2 to 30 carbon atoms having at least one aromaticring selected from the group consisting of an aromatic hydrocarbon ringand an aromatic heterocyclic ring, of A^(xw), may have a plurality ofaromatic rings, and may have an aromatic hydrocarbon ring and anaromatic heterocyclic ring.

Examples of the aromatic hydrocarbon ring may include a benzene ring, anaphthalene ring, and an anthracene ring. Examples of the aromaticheterocyclic ring may include a monocyclic aromatic heterocyclic ringsuch as a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring,a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring,an imidazole ring, an oxazole ring, and a thiazole ring; and a condensedaromatic heterocyclic ring such as a benzothiazole ring, a benzoxazolering, a quinoline ring, a phthalazine ring, a benzimidazole ring, abenzopyrazole ring, a benzofuran ring, a benzothiophene ring, athiazolopyridine ring, an oxazolopyridine ring, a thiazolopyrazine ring,an oxazolopyrazine ring, a thiazolopyridazine ring, an oxazolopyridazinering, a thiazolopyrimidine ring, and an oxazolopyrimidine ring.

The aromatic ring group of A^(xw) may have a substituent. Examples ofthe substituent may include a halogen atom such as a fluorine atom and achlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atomssuch as a methyl group, an ethyl group, and a propyl group; an alkenylgroup having 2 to 6 carbon atoms such as a vinyl group and an allylgroup; a halogenated alkyl group having 1 to 6 carbon atoms such as atrifluoromethyl group; a substituted amino group such as a dimethylaminogroup; an alkoxy group having 1 to 6 carbon atoms such as a methoxygroup, an ethoxy group, and an isopropoxy group; a nitro group; an arylgroup such as a phenyl group and a naphthyl group; —C(═O)—R^(5w);—C(═O)—OR^(5w); and —SO₂R^(6w). Herein, R^(5w) is an alkyl group having1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or acycloalkyl group having 3 to 12 carbon atoms, and R^(6w) is an alkylgroup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20carbon atoms, a phenyl group, or a 4-methylphenyl group, like R^(4w)which will be described later.

The aromatic ring of A^(xw) may have a plurality of substituents thatare the same or different, and two adjacent substituents may be bondedtogether to form a ring. The formed ring may be a monocyclic ring or acondensed polycyclic ring, and may be an unsaturated ring or a saturatedring.

The “number of carbon atoms” in the organic group having 2 to 30 carbonatoms of A^(xw) means the total number of carbon atoms in the entireorganic group, although carbon atoms in the substituents are excludedtherefrom (the same applies to A^(yw) which will be described later).

Examples of the organic group of 2 to 30 carbon atoms having at leastone aromatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring of A^(xw) may includean aromatic hydrocarbon ring group; an aromatic heterocyclic ring group;an alkyl group of 3 to 30 carbon atoms having at least one aromatic ringselected from the group consisting of an aromatic hydrocarbon ring groupand an aromatic heterocyclic ring group; an alkenyl group of 4 to 30carbon atoms having at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring group and an aromaticheterocyclic ring group; and an alkynyl group of 4 to 30 carbon atomshaving at least one aromatic ring selected from the group consisting ofan aromatic hydrocarbon ring group and an aromatic heterocyclic ringgroup.

Specific preferable examples of A^(xw) are as follows. However, in thepresent invention, A^(xw) is not limited to the following examples. Inthe following formulae, [—] represents an atomic bond extended from anyposition of the ring (the same applies to the following).

(1) An Aromatic Hydrocarbon Ring Group

(2) An Aromatic Heterocyclic Ring Group

In the formulae, E^(w) is NR^(6w), an oxygen atom, or a sulfur atom.Herein, R^(6w) is a hydrogen atom; or an alkyl group having 1 to 6carbon atoms such as a methyl group, an ethyl group, and a propyl group.

In the formulae, X^(w), Y^(w), and Z^(w) are each independently NR^(7w),an oxygen atom, a sulfur atom, —SO—, or —SO₂— (provided that a casewhere oxygen atoms, sulfur atoms, —SO— groups, or —SO₂— groups areadjacent is excluded). R^(7w) is a hydrogen atom; or an alkyl grouphaving 1 to 6 carbon atoms such as a methyl group, an ethyl group, and apropyl group, like the aforementioned R^(6w).

(In the formulae, X^(w) has the same meanings as described above.)

(3) An alkyl group having at least one aromatic ring selected from thegroup consisting of an aromatic hydrocarbon ring group and an aromaticheterocyclic ring group

(4) An alkenyl group having at least one aromatic ring selected from thegroup consisting of an aromatic hydrocarbon ring group and an aromaticheterocyclic ring group

(5) An alkynyl group having at least one aromatic ring selected from thegroup consisting of an aromatic hydrocarbon ring group and an aromaticheterocyclic ring group

Among the groups of the aforementioned A^(xw), an aromatic hydrocarbongroup having 6 to 30 carbon atoms and an aromatic heterocyclic ringgroup having 4 to 30 carbon atoms are preferable. Any of the groupsshown in the following are more preferable.

Any of the groups shown in the following are further preferable.

The ring of A^(xw) may have a substituent. Examples of the substituentmay include a halogen atom such as a fluorine atom and a chlorine atom;a cyano group; an alkyl group having 1 to 6 carbon atoms such as amethyl group, an ethyl group, and a propyl group; an alkenyl grouphaving 2 to 6 carbon atoms such as a vinyl group and an allyl group; ahalogenated alkyl group having 1 to 6 carbon atoms such as atrifluoromethyl group; a substituted amino group such as a dimethylaminogroup; an alkoxy group having 1 to 6 carbon atoms such as a methoxygroup, an ethoxy group, and an isopropoxy group; a nitro group; an arylgroup such as a phenyl group and a naphthyl group; —C(═O)—OR^(8w);—C(═O)—OR^(8w); and —SO₂R^(6w). Herein, R^(8w) is an alkyl group having1 to 6 carbon atoms such as a methyl group or an ethyl group; or an arylgroup having 6 to 14 carbon atoms such as a phenyl group. Among these, ahalogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms,and an alkoxy group having 1 to 6 carbon atoms are preferable.

The ring of A^(xw) may have a plurality of substituents that are thesame or different, and two adjacent substituents may be bonded togetherto form a ring. The formed ring may be a monocyclic ring or a condensedpolycyclic ring.

The “number of carbon atoms” in the organic group having 2 to 30 carbonatoms of A^(xw) means the total number of carbon atoms in the entireorganic group, although carbon atoms in the substituents are excludedtherefrom (the same applies to A^(yw) which will be described later).

A^(yw) is a hydrogen atom, an alkyl group having 1 to 20 carbon atomsand optionally having a substituent, an alkenyl group having 2 to 20carbon atoms and optionally having a substituent, a cycloalkyl grouphaving 3 to 12 carbon atoms and optionally having a substituent, analkynyl group having 2 to 20 carbon atoms and optionally having asubstituent, —C(═O)—R^(3w), —SO₂—R^(4w), —C(═S)NH—R^(9w), or an organicgroup having 2 to 30 carbon atoms and at least one aromatic ringselected from the group consisting of an aromatic hydrocarbon ring andan aromatic heterocyclic ring. Herein, R^(3w) is an alkyl group having 1to 20 carbon atoms and optionally having a substituent, an alkenyl grouphaving 2 to 20 carbon atoms and optionally having a substituent, acycloalkyl group having 3 to 12 carbon atoms and optionally having asubstituent, or an aromatic hydrocarbon group having 5 to 12 carbonatoms, R^(4w) is an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenylgroup, and R^(9w) is an alkyl group having 1 to 20 carbon atoms andoptionally having a substituent, an alkenyl group having 2 to 20 carbonatoms and optionally having a substituent, a cycloalkyl group having 3to 12 carbon atoms and optionally having a substituent, or an aromaticgroup having 5 to 20 carbon atoms and optionally having a substituent.

Examples of an alkyl group having 1 to 20 carbon atoms in the alkylgroup having 1 to 20 carbon atoms and optionally having a substituent ofA^(yw) may include a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, an isobutyl group, a 1-methylpentylgroup, a 1-ethylpentyl group, a sec-butyl group, a tert-butyl group, an-pentyl group, an isopentyl group, a neopentyl group, a n-hexyl group,an isohexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, an-decyl group, a n-undecyl group, a n-dodecyl group, a n-tridecyl group,a n-tetradecyl group, a n-pentadecyl group, a n-hexadecyl group, an-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, and an-icosyl group. The number of carbon atoms in the alkyl group having 1to 20 carbon atoms and optionally having a substituent is preferably 1to 12, and further preferably 4 to 10.

Examples of an alkenyl group having 2 to 20 carbon atoms in the alkenylgroup having 2 to 20 carbon atoms and optionally having a substituent ofA^(yw) may include a vinyl group, a propenyl group, an isopropenylgroup, a butenyl group, an isobutenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a decenyl group, an undecenylgroup, a dodecenyl group, a tridecenyl group, a tetradecenyl group, apentadecenyl group, a hexadecenyl group, a heptadecenyl group, anoctadecenyl group, a nonadecenyl group, and an icocenyl group.

The number of carbon atoms in the alkenyl group having 2 to 20 carbonatoms and optionally having a substituent is preferably 2 to 12.

Examples of a cycloalkyl group having 3 to 12 carbon atoms in thecycloalkyl group having 3 to 12 carbon atoms and optionally having asubstituent of A^(yw) may include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

Examples of an alkynyl group having 2 to 20 carbon atoms in the alkynylgroup having 2 to 20 carbon atoms and optionally having a substituent ofA^(yw) may include an ethynyl group, a propynyl group, a 2-propynylgroup (propargyl group), a butynyl group, a 2-butynyl group, a 3-butynylgroup, a pentynyl group, a 2-pentynyl group, a hexynyl group, a5-hexynyl group, a heptynyl group, an octynyl group, a 2-octynyl group,a nonanyl group, a decanyl group, and a 7-decanyl group.

Examples of substituents in the alkyl group having 1 to 20 carbon atomsand optionally having a substituent and the alkenyl group having 2 to 20carbon atoms and optionally having a substituent of A^(yw) may include ahalogen atom such as a fluorine atom and a chlorine atom; a cyano group;a substituted amino group such as a dimethylamino group; an alkoxy grouphaving 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, anisopropoxy group, and a butoxy group; an alkoxy group having 1 to 12carbon atoms that is substituted by an alkoxy group having 1 to 12carbon atoms such as a methoxymethoxy group and a methoxyethoxy group; anitro group; an aryl group such as a phenyl group and a naphthyl group;a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropylgroup, a cyclopentyl group, and a cyclohexyl group; a cycloalkyloxygroup having 3 to 8 carbon atoms such as a cyclopentyloxy group and acyclohexyloxy group; a cyclic ether group having 2 to 12 carbon atomssuch as a tetrahydrofuranyl group, a tetrahydropyranyl group, adioxolanyl group, and a dioxanyl group; an aryloxy group having 6 to 14carbon atoms such as a phenoxy group and a naphthoxy group; afluoroalkoxy group having 1 to 12 carbon atoms having at least onesubstitution by a fluorine atom, such as a trifluoromethyl group, apentafluoroethyl group, and —CH₂CF₃; a benzofuryl group; a benzopyranylgroup; a benzodioxolyl group; a benzodioxanyl group; —C(═O)—R^(7w);—C(═O)—OR^(7w); —SO₂R^(8w); —SR^(10w); an alkoxy group having 1 to 12carbon atoms that is substituted by —SR^(10w); and a hydroxyl group.Herein, R^(7w) and R^(10w) are each independently an alkyl group having1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, acycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbongroup having 6 to 12 carbon atoms, and R^(8w) is an alkyl group having 1to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, aphenyl group, or a 4-methylphenyl group, like the aforementioned R^(4w).

Examples of a substituent in the cycloalkyl group having 3 to 12 carbonatoms and optionally having a substituent of A^(yw) may include ahalogen atom such as a fluorine atom and a chlorine atom; a cyano group;a substituted amino group such as a dimethylamino group; an alkyl grouphaving 1 to 6 carbon atoms such as a methyl group, an ethyl group, and apropyl group; an alkoxy group having 1 to 6 carbon atoms such as amethoxy group, an ethoxy group, and an isopropoxy group; a nitro group;an aryl group such as a phenyl group and a naphthyl group; a cycloalkylgroup having 3 to 8 carbon atoms such as a cyclopropyl group, acyclopentyl group, and a cyclohexyl group; —C(═O)—R^(7w);—C(═O)—OR^(7w); —SO₂R^(8w); and a hydroxyl group. Herein, R^(7w) andR^(8w) have the same meanings as described above.

Examples of a substituent in the alkynyl group having 2 to 20 carbonatoms and optionally having a substituent of A^(yw) may includesubstituents that are the same as the substituents in the alkyl grouphaving 1 to 20 carbon atoms and optionally having a substituent and thealkenyl group having 2 to 20 carbon atoms and optionally having asubstituent.

In the group represented by —C(═O)—R^(3w) of A^(yw), R^(3w) is an alkylgroup having 1 to 20 carbon atoms and optionally having a substituent,an alkenyl group having 2 to 20 carbon atoms and optionally having asubstituent, a cycloalkyl group having 3 to 12 carbon atoms andoptionally having a substituent, or an aromatic hydrocarbon group having5 to 12 carbon atoms. Specific examples thereof may include thoseexemplified as the examples of the alkyl group having 1 to 20 carbonatoms and optionally having a substituent, the alkenyl group having 2 to20 carbon atoms and optionally having a substituent, and the cycloalkylgroup having 3 to 12 carbon atoms and optionally having a substituent ofA^(yw).

In the group represented by —SO₂—R^(4w) of A^(yw), R^(4w) is an alkylgroup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20carbon atoms, a phenyl group or a 4-methylphenyl group.

Specific examples of the alkyl group having 1 to 20 carbon atoms and thealkenyl group having 2 to 20 carbon atoms of R^(4w) may include thoseexemplified as the examples of the alkyl group having 1 to 20 carbonatoms and the alkenyl group having 2 to 20 carbon atoms of theaforementioned A^(yw).

Examples of the organic group having 2 to 30 carbon atoms and at leastone aromatic ring selected from the group consisting of an aromatichydrocarbon ring and an aromatic heterocyclic ring of A^(yw) may includethose exemplified as the examples regarding A^(xw).

Among these, it is preferable that A^(yw) is a group represented by ahydrogen atom, an alkyl group having 1 to 20 carbon atoms and optionallyhaving a substituent, an alkenyl group having 2 to 20 carbon atoms andoptionally having a substituent, a cycloalkyl group having 3 to 12carbon atoms and optionally having a substituent, an alkynyl grouphaving 2 to 20 carbon atoms and optionally having a substituent,—C(═O)—R^(3w), —SO₂—R^(4w), or an organic group having 2 to 30 carbonatoms and at least one aromatic ring selected from the group consistingof an aromatic hydrocarbon ring and an aromatic heterocyclic ring, andfurther preferably a group represented by a hydrogen atom, an alkylgroup having 1 to 20 carbon atoms and optionally having a substituent,an alkenyl group having 2 to 20 carbon atoms and optionally having asubstituent, a cycloalkyl group having 3 to 12 carbon atoms andoptionally having a substituent, an alkynyl group having 2 to 20 carbonatoms and optionally having a substituent, an aromatic hydrocarbon grouphaving 6 to 12 carbon atoms and optionally having a substituent, anaromatic heterocyclic ring group having 3 to 9 carbon atoms andoptionally having a substituent, —C(═O)—R^(3w), or —SO₂—R^(4w). Herein,R^(3w) and R^(4w) have the same meanings as described above.

It is preferable that substituents in the alkyl group having 1 to 20carbon atoms and optionally having a substituent, the alkenyl grouphaving 2 to 20 carbon atoms and optionally having a substituent, and thealkynyl group having 2 to 20 carbon atoms and optionally having asubstituent of A^(yw) are a halogen atom, a cyano group, an alkoxy grouphaving 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atomsthat is substituted by an alkoxy group having 1 to 12 carbon atoms, aphenyl group, a cyclohexyl group, a cyclic ether group having 2 to 12carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxylgroup, a benzodioxanyl group, a phenylsulfonyl group, a4-methylphenylsulfonyl group, a benzoyl group, or —SR^(10w). Herein,R^(10w) has the same meanings as described above.

It is preferable that substituents in the cycloalkyl group having 3 to12 carbon atoms and optionally having a substituent, the aromatichydrocarbon group having 6 to 12 carbon atoms and optionally having asubstituent, and the aromatic heterocyclic ring group having 3 to 9carbon atoms and optionally having a substituent of A^(yw) are afluorine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxygroup having 1 to 6 carbon atoms, or a cyano group.

A^(xw) and A^(yw) may together form a ring. Examples of the ring mayinclude an unsaturated heterocyclic ring having 4 to 30 carbon atoms andan unsaturated carbon ring having 6 to 30 carbon atoms, wherein theserings may optionally have a substituent.

The unsaturated heterocyclic ring having 4 to 30 carbon atoms and theunsaturated carbon ring having 6 to 30 carbon atoms are not particularlyrestricted, and may or may not have aromaticity. Examples thereof mayinclude rings shown in the following. The rings shown in the followingare a moiety of:

in the formula (I)

(In the formulae, X^(w), Y^(w), and Z^(w) have the same meanings asdescribed above.) The rings may have a substituent. Examples of thesubstituent may include those exemplified as the examples of thesubstituent on the aromatic ring of A^(xw).

The total number of π electrons included in A^(xw) and A^(yw) ispreferably 4 or more and 24 or less, more preferably 6 or more and 20 orless, and further preferably 6 or more and 18 or less from the viewpointof favorably expressing the desired effect of the present invention.

Examples of preferred combination of A^(xw) and A^(yw) may include:

(α) a combination of A^(xw) and A^(yw) in which A^(xw) is an aromatichydrocarbon group or an aromatic heterocyclic ring group having 4 to 30carbon atoms, A^(yw) is a hydrogen atom, a cycloalkyl group having 3 to8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbonatoms and optionally having (a halogen atom, a cyano group, an alkylgroup having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbonatoms, or a cycloalkyl group having 3 to 8 carbon atoms) as asubstituent, an aromatic heterocyclic ring group having 3 to 9 carbonatoms and optionally having (a halogen atom, an alkyl group having 1 to6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyanogroup) as a substituent, an alkyl group having 1 to 20 carbon atoms andoptionally having a substituent, an alkenyl group having 1 to 20 carbonatoms and optionally having a substituent, or an alkynyl group having 2to 20 carbon atoms and optionally having a substituent, and thesubstituent is any of a halogen atom, a cyano group, an alkoxy grouphaving 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atomsthat is substituted by an alkoxy group having 1 to 12 carbon atoms, aphenyl group, a cyclohexyl group, a cyclic ether group having 2 to 12carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxylgroup, a benzodioxanyl group, a benzenesulfonyl group, a benzoyl group,and —SR^(10w); and

(β) a combination in which A^(xw) and A^(yw) together form anunsaturated heterocyclic ring or an unsaturated carbon ring.

Herein, R^(10w) has the same meanings as described above.

Examples of more preferred combination of A^(xw) and A^(yw) may include:

(γ) a combination in which A^(xw) is any of groups having the followingstructures, A^(yw) is a hydrogen atom, a cycloalkyl group having 3 to 8carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atomsand optionally having (a halogen atom, a cyano group, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or a cycloalkyl group having 3 to 8 carbon atoms) as a substituent, anaromatic heterocyclic ring group having 3 to 9 carbon atoms andoptionally having (a halogen atom, an alkyl group having 1 to 6 carbonatoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group) asa substituent, an alkyl group having 1 to 20 carbon atoms and optionallyhaving a substituent, an alkenyl group having 1 to 20 carbon atoms andoptionally having a substituent, or an alkynyl group having 2 to 20carbon atoms and optionally having a substituent, and the substituent isany of a halogen atom, a cyano group, an alkoxy group having 1 to 20carbon atoms, an alkoxy group having 1 to 12 carbon atoms that issubstituted by an alkoxy group having 1 to 12 carbon atoms, a phenylgroup, a cyclohexyl group, a cyclic ether group having 2 to 12 carbonatoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxyl group, abenzodioxanyl group, a benzenesulfonyl group, a benzoyl group, and—SR^(10w). Herein, R^(10w) has the same meanings as described above.

(In the formulae, X^(w) and Y^(w) have the same meanings as describedabove.)

A particularly preferred combination of A^(xw) and A^(yw) is (δ) acombination in which A^(xw) is any of groups having the followingstructures, A^(yw) is a hydrogen atom, a cycloalkyl group having 3 to 8carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atomsand optionally having (a halogen atom, a cyano group, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or a cycloalkyl group having 3 to 8 carbon atoms) as a substituent, anaromatic heterocyclic ring group having 3 to 9 carbon atoms andoptionally having (a halogen atom, an alkyl group having 1 to 6 carbonatoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group) asa substituent, an alkyl group having 1 to 20 carbon atoms and optionallyhaving a substituent, an alkenyl group having 1 to 20 carbon atoms andoptionally having a substituent, or an alkynyl group having 2 to 20carbon atoms and optionally having a substituent, and the substituent isany of a halogen atom, a cyano group, an alkoxy group having 1 to 20carbon atoms, an alkoxy group having 1 to 12 carbon atoms that issubstituted by an alkoxy group having 1 to 12 carbon atoms, a phenylgroup, a cyclohexyl group, a cyclic ether group having 2 to 12 carbonatoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxyl group, abenzodioxanyl group, a benzenesulfonyl group, a benzoyl group, and—SR^(10w). In the following formulae, X has the same meanings asdescribed above. Herein, R^(10w) has the same meanings as describedabove.

A^(1w) is a trivalent aromatic group optionally having a substituent.The trivalent aromatic group may be a trivalent carbocyclic aromaticgroup or a trivalent heterocyclic aromatic group. From the viewpoint offavorably expressing the desired effect of the present invention, thetrivalent carbocyclic aromatic group is preferable, a trivalent benzenering group and a trivalent naphthalene ring group are more preferable,and a trivalent benzene ring group and a trivalent naphthalene ringgroup represented by the following formulae are further preferable.

In the following formulae, substituents Y^(1w) and Y^(2w) are shown forthe sake of convenience to clearly show a bonding state (Y^(1w) andY^(2w) have the same meanings as described above, and the same appliedto the following).

In particular, it is preferable that A^(1w) is a group represented byeach of the formulae (A^(w)11) to (A^(w)25), more preferably a grouprepresented by the formula (A^(w)11), (A^(w)13), (A^(w)15), (A^(w)19),or (A^(w)23), and particularly preferably a group represented by theformula (A^(w)11) or (A^(w)23)

Examples of a substituent that may be included in the trivalent aromaticgroup of A^(1w) may include those exemplified as the examples of thesubstituent on the aromatic group of the aforementioned A^(Xw). It ispreferable that A^(1w) is a trivalent aromatic group having nosubstituent.

A^(2w) and A^(3w) are each independently a divalent alicyclichydrocarbon group having 3 to 30 carbon atoms and optionally having asubstituent.

Examples of the divalent alicyclic hydrocarbon group having 3 to 30carbon atoms may include a cycloalkanediyl group having 3 to 30 carbonatoms and a divalent alicyclic condensed ring group having 10 to 30carbon atoms.

Examples of the cycloalkanediyl group having 3 to 30 carbon atoms mayinclude a cyclopropanediyl group; a cyclobutanediyl group such as acyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group; acyclopentanediyl group such as a cyclopentane-1,2-diyl group and acyclopentane-1,3-diyl group; a cyclohexanediyl group such as acyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and acyclohexane-1,4-diyl group; a cycloheptanediyl group such as acycloheptane-1,2-diyl group, a cycloheptane-1,3-diyl group, and acycloheptane-1,4-diyl group; a cyclooctanediyl group such as acyclooctane-1,2-diyl group, a cyclooctane-1,3-diyl group, acyclooctane-1,4-diyl group, and a cyclooctane-1,5-diyl group; acyclodecanediyl group such as a cyclodecane-1,2-diyl group, acyclodecane-1,3-diyl group, a cyclodecane-1,4-diyl group, and acyclodecane-1,5-diyl group; a cyclododecanediyl group such as acyclododecane-1,2-diyl group, a cyclododecane-1,3-diyl group, acyclododecane-1,4-diyl group, and a cyclododecane-1,5-diyl group; acyclotetradecanediyl group such as a cyclotetradecane-1,2-diyl group, acyclotetradecane-1,3-diyl group, a cyclotetradecane-1,4-diyl group, acyclotetradecane-1,5-diyl group, and a cyclotetradecane-1,7-diyl group;and a cycloeicosanediyl group such as a cycloeicosane-1,2-diyl group anda cycloeicosane-1,10-diyl group.

Examples of the divalent alicyclic condensed ring group having 10 to 30carbon atoms may include a decalindiyl group such as a decalin-2,5-diylgroup and a decalin-2,7-diyl group; an adamantanediyl group such as anadamantane-1,2-diyl group and an adamantane-1,3-diyl group; and abicyclo[2.2.1]heptanediyl group such as a bicyclo[2.2.1]heptane-2,3-diylgroup, a bicyclo[2.2.1]heptane-2,5-diyl group, and abicyclo[2.2.1]heptane-2,6-diyl group.

The divalent alicyclic hydrocarbon groups may further have a substituenton any position. Examples of the substituent may include thoseexemplified as the examples of the substituent on the aromatic ring ofthe aforementioned A^(xw).

Among these, it is preferable that A^(2w) and A^(3w) are a divalentalicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferablya cycloalkanediyl group having 3 to 12 carbon atoms, further preferablya group represented by each of the following formulae (A^(w)31) to(A^(w)34):

and particularly preferably the group represented by the formula(A^(w)32).

As the divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms,there may exist cis- and trans-stereoisomers on the basis of differenceof steric configuration of carbon atom bonded to Y^(1w) and Y^(3w) (orY^(2w) and Y^(4w)). For example, when the group is acyclohexane-1,4-diyl group, a cis-isomer (A^(w)32a) and a trans-isomer(A^(w)32 b) can exist, as described in the following.

In the present invention, the group may be a cis-isomer, a trans-isomer,or an isomeric mixture of cis- and trans-isomers. The trans-isomer andthe cis-isomer are preferable, and the trans-isomer is more preferablesince orientation is favorable.

A^(4w) and A^(5w) are each independently a divalent aromatic grouphaving 6 to 30 carbon atoms and optionally having a substituent.

The aromatic group of A^(4w) and A^(5w) may be monocyclic or polycyclic.

Specific preferable examples of A^(4w) and A^(5w) may include thefollowing groups.

The divalent aromatic group of the aforementioned A^(4w) and A^(5w) mayhave a substituent on any position. Examples of the substituent mayinclude a halogen atom, a cyano group, a hydroxyl group, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,a nitro group, and a —C(═O)—OR^(8w) group. Herein, R^(8w) is an alkylgroup having 1 to 6 carbon atoms. Among these, a halogen atom, an alkylgroup having 1 to 6 carbon atoms, and an alkoxy group are preferable.Among the halogen atom, a fluorine atom is more preferable, among thealkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group,and a propyl group are more preferable, and among the alkoxy group, amethoxy group and an ethoxy group are more preferable.

Among these, it is preferable that A^(4w) and A^(5w) are independently agroup represented by the following formulae (A^(w)41), (A^(w)42), and(A^(w)43) and that may optionally have a substituent from the viewpointof favorably expressing the desired effect of the present invention, andthe group represented by the formula (A^(w)41) and optionally having asubstituent is particularly preferable.

Q^(1w) is a hydrogen atom or an alkyl group having 1 to 6 carbon atomsand optionally having a substituent.

Examples of the alkyl group having 1 to 6 carbon atoms and optionallyhaving a substituent may include those exemplified as the examplesregarding the aforementioned A^(xw).

Among these, Q^(1w) is preferably a hydrogen atom or an alkyl grouphaving 1 to 6 carbon atoms, and more preferably a hydrogen atom or amethyl group.

The compound (V) may be produced by, e.g., the following reaction.

(wherein Y^(1w) to Y^(8w), G^(1w), G^(2w), Z^(1w), Z^(2w), A^(xw),A^(yw), A^(1w) to A^(5w), and Q^(1w) have the same meanings as describedabove.)

Specifically, a hydrazine compound represented by the formula (3w)(hydrazine compound (3w)) may be reacted with a carbonyl compoundrepresented by the formula (4w) (carbonyl compound (4w)) at a molarratio of [hydrazine compound (3w):carbonyl compound (4w)] of 1:2 to 2:1,and preferably 1:1.5 to 1.5:1 to highly selectively produce a targetcompound (V) in high yield.

In this case, an acid catalyst, such as an organic acid such as(±)-10-camphorsulfonic acid and p-toluene sulfonic acid; and aninorganic acid such as hydrochloric acid and sulfuric acid, may be addedto perform the reaction. The addition of the acid catalyst may shortenthe reaction time and may improve the yield. The amount of the acidcatalyst to be added is usually 0.001 to 1 mol relative to 1 mol of thecarbonyl compound (4w). The acid catalyst may be added as it is, or in asolution form in which the acid catalyst is dissolved in an appropriatesolution.

The solvent used in the reaction is not particularly limited so long asit is inert to the reaction. Examples of the solvent may include analcohol solvent such as methyl alcohol, ethyl alcohol, n-propyl alcohol,isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,and tert-butyl alcohol; an ether solvent such as diethyl ether,tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, and cyclopentylmethyl ether; an ester solvent such as ethyl acetate, propyl acetate,and methyl propionate; an aromatic hydrocarbon-based solvent such asbenzene, toluene, and xylene; an aliphatic hydrocarbon-based solventsuch as n-pentane, n-hexane, and n-heptane; an amide-based solvent suchas N,N-dimethylformamide, N-methylpyrrolidone, and triamidehexamethylphosphate; a sulfur-containing solvent such as dimethylsulfoxide and sulfolane; and a mixed solvent of two or more typesthereof.

Among these, the alcohol solvent, the ether solvent, and a mixed solventof the alcohol solvent and the ether solvent are preferable.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 100 g relative to1 g of the hydrazine compound (3w).

The reaction smoothly proceeds in a temperature range of −10° C. to theboiling point of the solvent to be used. The reaction time of eachreaction may vary depending on the reaction scale, and is usuallyseveral minutes to several hours.

The hydrazine compound (3w) may be produced as follows.

(wherein A^(xw) and A^(yw) have the same meanings as described above.X^(w) is a leaving group such as a halogen atom, a methanesulfonyloxygroup, and a p-toluenesulfonyloxy group.)

Specifically, a compound represented by the formula (2wa) may be reactedwith hydrazine (1w) in an appropriate solvent at a molar ratio of(compound (2wa) hydrazine (1w)) of 1:1 to 1:20, and preferably 1:2 to1:10, to obtain a corresponding hydrazine compound (3wa). Further, thehydrazine compound (3wa) may be reacted with a compound represented bythe formula (2wb) to obtain the hydrazine compound (3w).

As hydrazine (1w), hydrazine monohydrate is usually used. As hydrazine(1w), a commercially available product may be used as it is.

The solvent used in the reaction is not particularly limited as long asit is inert to the reaction. Examples of the solvent may include analcohol solvent such as methyl alcohol, ethyl alcohol, n-propyl alcohol,isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol,and tert-butyl alcohol; an ether solvent such as diethyl ether,tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, and cyclopentylmethyl ether; an aromatic hydrocarbon-based solvent such as benzene,toluene, and xylene; an aliphatic hydrocarbon-based solvent such asn-pentane, n-hexane, and n-heptane; an amide-based solvent such asN,N-dimethylformamide, N-methylpyrrolidone, and triamidehexamethylphosphate; a sulfur-containing solvent such as dimethylsulfoxide and sulfolane; and a mixed solvent of two or more typesthereof.

Among these, the alcohol solvent, the ether solvent, and a mixed solventof the alcohol solvent and the ether solvent are preferable.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 100 g relative to1 g of hydrazine.

The reaction smoothly proceeds in a temperature range of −10° C. to theboiling point of the solvent to be used. The reaction time of eachreaction may vary depending on the reaction scale, and is usuallyseveral minutes to several hours.

The hydrazine compound (3w) may also be produced by reducing a diazoniumsalt (5w) through a publicly known method, as described in thefollowing.

In the formula (5), A^(xw) and A^(yw) have the same meanings asdescribed above. X^(w−) is an anion that is a counter ion of diazonium.Examples of X^(w−) may include an inorganic anion such as ahexafluorophosphate ion, a fluoroborate ion, a chloride ion, and asulfate ion; and an organic anion such as a polyfluoroalkyl carboxylateion, a polyfluoroalkyl sulfonate ion, a tetraphenyl borate ion, anaromatic carboxylate ion, and an aromatic sulfonate ion.

Examples of the reducing agent used in the reaction may include a metalsalt reducing agent.

The metal salt reducing agent is generally a compound containinglow-valent metal or a compound having a metal ion and a hydride source(see “Yuki Gosei Jikken-hou Handbook (Organic synthesis experimentalmethod handbook)”, 1990, edited by The Society of Synthetic OrganicChemistry, Japan, published by Maruzen Co., Ltd., p. 810).

Examples of the metal salt reducing agent may include NaAlH₄,NaAlH_(p)(Or)_(q) (wherein p and q are each independently an integer of1 to 3, p+q is 4, and r is an alkyl group having 1 to 6 carbon atoms),LiAlH₄, iBu₂AlH, LiBH₄, NaBH₄, SnCl₂, CrCl₂, and TiCl₃.

In the reduction reaction, a known reaction condition may be adopted.For example, the reaction may be carried out under a condition describedin Publications such as Japanese Patent Application Laid-Open No.2005-336103 A, “Shin Jikken Kagaku Koza (New course of experimentalchemistry)”, 1978, published by Maruzen Co., Ltd., vol. 14, and “JikkenKagaku Koza (Course of experimental chemistry)”, 1992, published byMaruzen Co., Ltd., vol. 20.

The diazonium salt (5^(w)) may be produced from a compound such asaniline by a conventional method.

The carbonyl compound (4^(w)) may be typically produced by appropriatelybonding and modifying a plurality of known compounds having a desiredstructure through any combination of reactions of forming an etherlinkage (—O—), an ester linkage (—C(═O)—O— and —O—C(═O)—), a carbonatelinkage (—O—C(═O)—O—), and an amide linkage (—C(═O)NH— and —NH—C(═O)—).

An ether linkage may be formed, e.g., as follows.

(i) A compound represented by the formula: D1-hal (hal represents ahalogen atom, and the same applies to the following) and a compoundrepresented by the formula: D2-OMet (Met represents an alkaline metal(mainly sodium), and the same applies to the following) are mixed andcondensed (Williamson synthesis). In the formulae, D1 and D2 areoptional organic groups (the same applies to the following).

(ii) A compound represented by the formula: D1-hal and a compoundrepresented by the formula: D2-OH are mixed in the presence of a basesuch as sodium hydroxide or potassium hydroxide and condensed.

(iii) A compound represented by the formula: D1-J (J represents an epoxygroup) and a compound represented by the formula: D2-OH are mixed in thepresence of a base such as sodium hydroxide or potassium hydroxide andcondensed.

(iv) A compound represented by the formula: D1-OFN (OFN represents agroup having an unsaturated bond) and a compound represented by theformula: D2-OMet are mixed in the presence of a base such as sodiumhydroxide or potassium hydroxide and subjected to an addition reaction.

(v) A compound represented by the formula: D1-hal and a compoundrepresented by the formula: D2-OMet are mixed in the presence of copperor cuprous chloride and condensed (Ullmann condensation).

An ester linkage and an amide linkage may be formed, e.g., as follows.

(vi) A compound represented by the formula: D1-COOH and a compoundrepresented by the formula: D2-OH or D2-NH₂ are subjected to dehydrationcondensation in the presence of a dehydration condensation agent(N,N-dicyclohexylcarbodiimide, etc.).

(vii) A compound represented by the formula: D1-COOH is reacted with ahalogenating agent to obtain a compound represented by the formula:D1-CO-hal, and the compound is reacted with a compound represented bythe formula: D2-OH or D2-NH₂ in the presence of a base.

(viii) A compound represented by the formula: D1-COOH is reacted with anacid anhydride to obtain a mixed acid anhydride, and the mixed acidanhydride is reacted with a compound represented by the formula: D2-OHor D2-NH₂.

(ix) A compound represented by the formula: D1-COOH and a compoundrepresented by the formula: D2-OH or D2-NH₂ are subjected to dehydrationcondensation in the presence of an acid catalyst or a base catalyst.

The carbonyl compound (4w) of the present invention may be morespecifically produced through a process shown in the following reactionformula.

(wherein Y^(1w) to Y^(8w), G^(1w), G^(2w), Z^(1w), Z^(2w), A^(1w) toA^(5w), and Q^(1w) have the same meanings as described above. L^(1w) andL^(2w) are a leaving group such as a hydroxyl group, a halogen atom, amethanesulfonyloxy group, and a p-toluenesulfonyloxy group. —Y^(1aw) isa group that forms —Y^(1w)— as a result of the reaction with -L^(1w),and —Y^(2aw) is a group that forms —Y^(2w)— as a result of the reactionwith -L^(2w).)

That is, by using a publicly known reaction of forming an ether linkage(—O—), an ester linkage (—C(═O)—O— and —O—C(═O)—), or a carbonatelinkage (—O—C(═O)—O—), the carbonyl compound (4w) of the presentinvention may be produced by reacting a compound represented by theformula (6wd) with a compound represented by the formula (7wa) and thenreacting with a compound represented by the formula (7wb).

More specifically, a method for producing a compound (4w′) whereinY^(1w) is a group represented by a Y^(11w)—C(═O)—O— group and a grouprepresented by a formula ofZ^(2w)—Y^(8w)-G^(2w)-Y^(6w)-A^(5w)-Y^(4w)-A^(3w)-Y^(2w)— is the same asa group represented by a formula ofZ^(1w)—Y^(7w)-G^(1w)-Y^(5w)-A^(4w)-Y^(3w)-A^(2w)-Y^(1w)— is as follows.

(wherein Y^(3w), Y^(5w), Y^(7w), G^(1w), Z^(1w), A^(1w), A^(2w), A^(4w),Q^(1w), and L^(1w) have the same meanings as described above. Y^(11w) isa group having a structure such that Y^(11w)—C(═O)—O— corresponds toY^(1w). Y^(1w) has the same meanings as described above.)

In the reaction, a dihydroxy compound represented by the formula (6w)(compound (6w)) may be reacted with a compound represented by theformula (7w) (compound (7w)) at a molar ratio of (compound (6w):compound(7w)) of 1:2 to 1:4, and preferably 1:2 to 1:3 to highly selectivelyproduce a target compound (4w′) in high yield.

When the compound (7w) is a compound in which L^(1w) in the formula (7w)is a hydroxyl group (carboxylic acid), the reaction may be carried outin the presence of a dehydration condensation agent such as1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride ordicyclohexyl carbodiimide to obtain a target compound.

The amount of the dehydration condensation agent to be used is usually 1to 3 mol relative to 1 mol of the compound (7w).

When the compound (7w) is a compound in which L^(1w) in the formula (7w)is a hydroxyl group (carboxylic acid), the reaction may be carried outin the presence of sulfonyl halide such as methanesulfonyl chloride orp-toluenesulfonyl chloride and a base such as triethylamine,diisopropylethylamine, pyridine, or 4-(dimethylamino)pyridine, to obtaina target compound.

The amount of the sulfonyl halide to be used is usually 1 to 3 molrelative to 1 mol of the compound (7w).

The amount of the base to be used is usually 1 to 3 mol relative to 1mol of the compound (7w).

In this case, the compound in which L^(1w) in the formula (7w) is asulfonyloxy group (mixed acid anhydride) may be isolated, to perform thesubsequent reaction.

When the compound (7w) is a compound in which L^(1w) in the formula (7w)is a halogen atom (acid halide), the reaction may be carried out in thepresence of a base to obtain a target compound.

Examples of the base for use may include an organic base such astriethylamine and pyridine; and an inorganic base such as sodiumhydroxide, sodium carbonate, and sodium hydrogen carbonate.

The amount of the base to be used is usually 1 to 3 mol relative to 1mol of the compound (7w).

Examples of the solvent used in the reaction may include a chlorinatedsolvent such as chloroform and methylene chloride; an amide-basedsolvent such as N-methyl pyrrolidone, N,N-dimethyl formamide,N,N-dimethyl acetamide, and triamide hexamethylphosphate; an ether suchas 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,tetrahydropyran, and 1,3-dioxolan; a sulfur-containing solvent such asdimethyl sulfoxide and sulfolane; an aromatic hydrocarbon-based solventsuch as benzene, toluene, and xylene; an aliphatic hydrocarbon-basedsolvent such as n-pentane, n-hexane, and n-octane; an alicyclichydrocarbon-based solvent such as cyclopentane and cyclohexane; and amixed solvent of two or more types thereof.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 50 g relative to1 g of the hydroxy compound (6).

Many of the compounds (6w) are known substances, and may be produced bya known method.

For example, the compound (6w) may be produced by a process shown in thefollowing reaction formula (see WO2009/042544 and the Journal of OrganicChemistry, 2011, 76, 8082-8087). A product commercially available as thecompound (6w) may also be used with optional purification process.

(wherein A^(1w) and Q^(1w) have the same meanings as described above,A^(1aw) represents a divalent aromatic group that is formylated oracylated to form A^(1w), and R^(w), represents a protecting group of ahydroxyl group such as an alkyl group having 1 to 6 carbon atoms such asa methyl group and an ethyl group and an alkoxyalkyl group having 2 to 6carbon atoms such as a methoxymethyl group.)

Specifically, the hydroxyl groups in the dihydroxy compound(1,4-dihydroxybenzene, 1,4-dihydroxynaphthalene, etc.) represented bythe formula (6wa) may be alkylated to obtain a compound represented bythe formula (6wb), the ortho position of the OR^(w), group may beformylated or acylated by a known method to obtain a compoundrepresented by the formula (6wc), and the compound may be deprotected(dealkylated) to obtain the target compound (6w).

The product commercially available as the compound (6w) may be used asit is or if desired, with purification.

Many of the compounds (7w) are known compounds, and may be produced byappropriately bonding and modifying a plurality of known compoundshaving a desired structure through any combination of reactions offorming an ether linkage (—O—), an ester linkage (—C(═O)—O— and—O—C(═O)—), a carbonate linkage (—O—C(═O)—O—), and an amide linkage(—C(═O)NH— and —NH—C(═O)—).

For example, when the compound (7w) is a compound represented by thefollowing formula (7w′) (compound (7w′)), the compound (7w) may beproduced as follows, using a dicarboxylic acid represented by theformula (9w′) (compound (9w′)).

(wherein Y^(5w), Y^(7w), G^(1w), Z^(1w), A^(2w), A^(4w), and Y^(11w)have the same meanings as described above. Y^(12w) is a group having astructure such that —O—C(═O)—Y^(12w) corresponds to Y^(3w). R^(w) is analkyl group such as a methyl group and an ethyl group; or an aryl groupoptionally having a substituent such as a phenyl group and ap-methylphenyl group.)

The compound (9w′) is first reacted with sulfonyl chloride representedby the formula (10w) in the presence of a base such as triethylamine or4-(dimethylamino)pyridine.

Subsequently, to the reaction mixture, a compound (8w) and a base suchas triethylamine or 4-(dimethylamino)pyridine are added to carry out areaction.

The amount of the sulfonyl chloride to be used is usually 0.5 to 0.7equivalent weight relative to 1 equivalent weight of the compound (9w′).

The amount of the compound (8w) to be used is usually 0.5 to 0.6equivalent weight relative to 1 equivalent weight of the compound (9w′).

The amount of the base to be used is usually 0.5 to 0.7 equivalentweight relative to 1 equivalent weight of the compound (3w).

The reaction temperature is 20 to 30° C., and the reaction time may varydepending on the reaction scale, or the like, and is several minutes toseveral hours.

Examples of the solvent used in the reaction may include thoseexemplified as the examples of the solvent that may be used forproduction of the compound (4w′). Among these, ethers are preferable.

The amount of the solvent to be used is not particularly limited, andmay be appropriately determined in consideration of type of compound tobe used and reaction scale. The amount is usually 1 to 50 g relative to1 g of the hydrazine compound (9w′).

In any of the reactions, a usual post-treatment operation in organicsynthesis chemistry may be carried out after completion of thereactions, and if desired, a known separation and purification operationsuch as column chromatography, recrystallization, and distillation maybe carried out to isolate a target compound.

The structure of the target compound may be identified by, e.g.,measurements such as of NMR spectrometry, IR spectrometry, and massspectrometry, as well as elemental analysis.

[1.5. Polymerizable Monomer]

The composition (A) contains a polymerizable monomer. In thisapplication, “polymerizable monomer” is, among compounds that havepolymerization ability and thus have capability of acting as a monomer,a compound that is particularly other than the polymerizable liquidcrystal compound with reverse wavelength dispersion.

As the polymerizable monomer, e.g., a compound having one or morepolymerizable groups per one molecule may be used. By having such apolymerizable group, polymerization can be achieved in formation of anoptically anisotropic layer. When the polymerizable monomer is acrosslinkable monomer having two or more polymerizable groups per onemolecule, a cross-linking polymerization can be achieved. Examples ofthe polymerizable groups may include groups that are the same as thegroups of Z¹—Y⁵— and Z²—Y⁶— in the compound (I), and specifically anacryloyl group, a methacryloyl group, and an epoxy group.

The polymerizable monomer usually has one or more mesogens per onemolecule, and is capable of being polymerized together with thepolymerizable liquid crystal compound with reverse wavelength dispersionin formation of the optically anisotropic layer. In the opticallyanisotropic layer formed by such polymerization, the mesogen of thepolymerizable monomer usually has wavelength dispersion property ofbirefringence Δn that is different from that of the polymerizable liquidcrystal compound with reverse wavelength dispersion.

In a preferred embodiment, the mesogen of the polymerizable monomer maybe a mesogen that is capable of being oriented in parallel to any one ofthe main chain mesogen and the side chain mesogen of the polymerizableliquid crystal compound with reverse wavelength dispersion. For example,the polymerizable monomer may have a mesogen of a structure similar toone of the main chain mesogen and the side chain mesogen of thepolymerizable liquid crystal compound with reverse wavelengthdispersion. By having such a mesogen, the polymerizable monomer can havewavelength dispersion property of birefringence Δn that is differentfrom that of the polymerizable liquid crystal compound with reversewavelength dispersion, and can be oriented in parallel to the main chainmesogen or the side chain mesogen of the polymerizable liquid crystalcompound with reverse wavelength dispersion.

Examples of the polymerizable monomer may include a compound representedby the following formula (II) and a compound represented by thefollowing formula (III) (they may be referred to hereinbelow as“compound (II)” and “compound (III), respectively”).

In the formula (II), Y¹ to Y⁶, G¹, G², Z¹, Z², and A¹ to A³ each havethe same meanings as described in description of the formula (I). R¹⁰ isa hydrogen atom or a methyl group. Y¹ to Y⁶, G¹, G², Z¹, Z², and A¹ toA³ in the structure of the compound (II) may be the same as or differentfrom corresponding groups in the co-used compound (I).

It is preferable that the mesogen moiety and the polymerizable groupmoiety of the compound (II) are the same as those in the co-usedcompound (I) in view of obtaining favorable orientation. Specifically,it is preferable that Y¹ to Y⁶, Z¹, Z², and A¹ to A³ in the compound(II) are in common with those in the compound (I).

Y^(1x) to Y^(6x), G^(1x), G^(2x), Z^(1x), Z^(2x), A^(xx), A^(yx), A^(1x)to A^(3x), and Q^(1x) in the formula (III) have the same meanings as Y¹to Y⁶, G¹, G², Z¹, Z², A^(x), A^(y), A¹ to A³, and Q¹, respectively, inthe formula (I). However, at least one of them is different from thecorresponding group in the co-used compound (I).

Specific examples of the compound (III) may include compounds in whichY^(1x) to Y^(6x), G^(1x), G^(2x), Z^(1x), Z^(2x), A^(xx), A^(yx), A^(2x)to A^(3x), and Q^(1x) in the formula (III) are the same as Y¹ to Y⁶, G¹,G², Z¹, Z², A^(x), A^(y), A² to A³, and Q¹, respectively, in the co-usedcompound (I) and A^(1x) is different from A¹ in the co-used compound(I). Specific examples of combination of the compound (I) and thecompound (III) may include a combination of the compounds (I) and (III)in which A¹ in the compound (I) is a group represented by the followingformula (A25), A^(1x) in the compound (III) is a group represented bythe following formula (A26), and other groups are the same as describedabove.

In the following, A¹ and A^(1x) are shown with Y¹ and Y² for the sake ofconvenience of illustration.

When the polymerizable monomer is the compound (II), the—Y³-A²-Y¹-A¹(R¹⁰)—Y²-A³-Y⁴— group acts as a mesogen. When thepolymerizable monomer is the compound (III), the—Y^(3x)-A^(2x)-Y^(1x)-A^(1x)-Y^(2x)-A^(3x)-Y^(4x)— group and the>A^(1x)-C(Q^(1x))=N—N(A^(XX))A^(yx) group acts as mesogens.

Specific examples of the compound (II) may include a compoundrepresented by the following formula

Specific examples of the compound (III) may include compoundsrepresented by the following formulae (III)-1 to (III)-4.

Other examples of the polymerizable monomer may include a compoundrepresented by the following formula (IV) (this may be referred tohereinbelow as “compound (IV)”).

The polymerizable monomer itself may have liquid crystallinity or mayhave non-liquid crystallinity. It is preferable that the polymerizablemonomer is a monomer having non-liquid crystallinity, and it isparticularly preferable that the monomer is the compound (III) havingnon-liquid crystallinity.

Herein, “non-liquid crystallinity” of the compound itself means thatwhen the polymerizable monomer itself is left at any temperature of roomtemperature to 200° C., the monomer does not exhibit orientation on asubstrate subjected to an orientation treatment. The presence or absenceof orientation is determined by the presence or absence of light-darkcontrast when a rubbing direction is rotated in a plane in cross-Nicoltransmission observation with a polarizing microscope.

The ratio of the polymerizable monomer in the composition (A) is usually1 to 100 parts by weight, and preferably 5 to 50 parts by weight,relative to 100 parts by weight of the polymerizable liquid crystalcompound with reverse wavelength dispersion. When the ratio of thepolymerizable monomer is appropriately adjusted to the range so as toexhibit desired reverse wavelength dispersion property, the reversewavelength dispersion property can be easily controlled with precision.

The polymerizable monomer may be produced by a known production method.When the polymerizable monomer has a structure similar to the compound(I), it may be produced in accordance with the method for producing thecompound (I).

[1.6. Other Components in Composition (A)]

In addition to the polymerizable liquid crystal compound with reversewavelength dispersion and the polymerizable monomer, the composition (A)may contain an optional component such as those exemplified in thefollowing, if necessary.

The composition (A) may contain an optional monomer copolymerizable withthe polymerizable liquid crystal compound with reverse wavelengthdispersion.

Examples of the optional monomer may include 4′-methoxyphenyl4-(2-methacryloyloxyethyloxyl)benzoate, biphenyl4-(6-methacryloyloxyhexyloxyl)benzoate, 4′-cyanobiphenyl4-(2-acryloyloxyethyloxyl)benzoate, 4′-cyanobiphenyl4-(2-methacryloyloxyethyloxyl)benzoate, 3′,4′-difluorophenyl4-(2-methacryloyloxyethyloxyl)benzoate, naphthyl4-(2-methacryloyloxyethyloxyl)benzoate, 4-acryloyloxy-4′-decylbiphenyl,4-acryloyloxy-4′-cyanobiphenyl,4-(2-acryloyloxyethyloxy)-4′-cyanobiphenyl,4-(2-methacryloyloxyethyloxy)-4′-methoxybiphenyl,4-(2-methacryloyloxyethyloxy)-4′-(4″-fluorobenzyloxy)-biphenyl,4-acryloyloxy-4′-propylcyclohexylphenyl,4-methacryloyl-4′-butylbicyclohexyl, 4-acryloyl-4′-amyltolan,4-acryloyl-4′-(3,4-difluorophenyl)bicyclohexyl, 4-amylphenyl4-(2-acryloyloxyethyloxyl)benzoate, and 4-(4′-propylcyclohexyl)phenyl4-(2-acyloyloxyethyl)benzoate.

As a commercially available product, LC-242 (product available fromBASF) may be used. Compounds disclosed in Japanese Patent ApplicationLaid-Open No. 2007-002208 A, Japanese Patent Application Laid-Open No.2009-173893 A, Japanese Patent Application Laid-Open No. 2009-274984 A,Japanese Patent Application Laid-Open No. 2010-030979 A, Japanese PatentApplication Laid-Open No. 2010-031223 A, and Japanese Patent ApplicationLaid-Open No. 2011-006360 A may also be used.

When the composition (A) contains an optional monomer, the ratio of theoptional monomer is preferably less than 50% by weight, and morepreferably 30% by weight or less, relative to the total of thepolymerizable liquid crystal compound with reverse wavelengthdispersion, the polymerizable monomer, and the optional monomer. Thelower limit of ratio of the optional monomer may be 0% by weight. Whenit falls within the range, the resulting optically anisotropic layer canhave a high glass transition temperature (Tg), and high membranehardness can be achieved. Therefore, this is preferable.

The composition (A) may contain a polymerization initiator. Thepolymerization initiator may be appropriately selected in accordancewith the type of polymerizable group in the polymerizable liquid crystalcompound with reverse wavelength dispersion, the polymerizable monomer,and the other polymerizable compound in the composition (A). Forexample, when the polymerizable group is radically polymerizable, aradical polymerization initiator may be used. When the polymerizablegroup is anionically polymerizable, an anionic polymerization initiatormay be used. When the polymerizable group is cationically polymerizable,a cationic polymerization initiator may be used.

As the radical polymerization initiator, any of a thermal radicalgenerator that is a compound that generates by heating an active speciescapable of initiating polymerization of the polymerizable compound; anda photoradical generator that is a compound that generates activespecies capable of initiating polymerization of the polymerizablecompound by exposure to exposure light such as visible light,ultraviolet light (i-line, etc.), far-ultraviolet light, electron beam,and X-ray may be used. The photoradical generator is suitably used.

Examples of the photoradical generator may include an acetophenone-basedcompound, a biimidazole-based compound, a triazine-based compound, anO-acyl oxime-based compound, an onium salt-based compound, abenzoin-based compound, a benzophenone-based compound, anα-diketone-based compound, a polynuclear quinone-based compound, axanthone-based compound, a diazo-based compound, and an imidesulfonate-based compound. These compounds serve as a component thatgenerates one or both of active radical and active acid by the lightexposure. One type of the photoradical generator may be used alone, ortwo or more types thereof may be used in combination.

Specific examples of the acetophenone-based compound may include2-hydroxy-2-methyl-1-phenylpropan-1-one,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one,1-hydroxycyclohexyl phenyl ketone,2,2-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione, and2-benzyl-2-dimethylamino-4′-morpholinobutylphenone.

Specific examples of the biimidazole-based compound may include2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole, and2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole.

When the biimidazole-based compound is used as the photopolymerizationinitiator, it is preferable that a hydrogen donor is used in combinationbecause the sensitivity is further improved.

“Hydrogen donor” means a compound capable of donating a hydrogen atom toa radical generated from the biimidazole-based compound by lightexposure. It is preferable that the hydrogen donor is a mercaptane-basedcompound or an amine-based compound, which will be defined as follows.

Examples of the mercaptane-based compound may include2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole,2,5-dimercapto-1,3,4-thiadizole, and2-mercapto-2,5-dimethylaminopyridine. Examples of the amine-basedcompound may include 4,4′-bis(dimethylamino)benzophenone,4,4′-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone,4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate,4-dimethylaminobenzoic acid, and 4-dimethylaminobenzonitrile.

Examples of the triazine-based compound may include a triazine-basedcompound having a halomethyl group such as2,4,6-tris(trichloromethyl)-s-triazine,2-methyl-4,6-bis(trichloromethyl)-s-triazine,2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

Specific examples of the O-acyl oxime-based compound may include1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime),1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime),1-[4-(benzoyl)phenyl]-octane-1,2-dione 2-(O-benzoyloxime),1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone1-(O-acetyloxime),1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-ethanone1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-ethanone1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime),andethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9.H.-carbazol-3-yl]-1-(O-acetyloxime).

As the photoradical generator, a commercially available product may beused as it is. Specific examples thereof may include trade name:Irgacure 907, trade name: Irgacure 184, trade name: Irgacure 369, tradename: Irgacure 651, trade name: Irgacure 819, trade name: Irgacure 907,and trade name: Irgacure OXE02, available from BASF, and trade name:ADEKA OPTOMER N1919 available from ADEKA CORPORATION.

Examples of the anionic polymerization initiator may include an alkyllithium compound; a monolithium salt or a monosodium salt of biphenyl,naphthalene, and pyrene; and a polyfunctional initiator such as adilithium salt and a trilithium salt.

Examples of the cationic polymerization initiator may include a proticacid such as sulfuric acid, phosphoric acid, perchloric acid, andtrifluoromethanesulfonic acid; Lewis acid such as boron trifluoride,aluminum chloride, titanium tetrachloride, and tin tetrachloride; and anaromatic onium salt, and a combination of an aromatic onium salt with areducing agent.

One type of the polymerization initiator may be used alone, or two ormore types thereof may be used in combination.

The ratio of the polymerization initiator in the composition (A) isusually 0.1 to 30 parts by weight, and preferably 0.5 to 10 parts byweight, relative to 100 parts by weight of the polymerizable compound.

The composition (A) may contain a surfactant for surface tensionadjustment. The surfactant is not particularly limited, and usually anonionic surfactant is preferable. As the nonionic surfactant, acommercially available product may be used. Examples thereof may includea nonionic surfactant that is an oligomer having a molecular weight ofseveral thousands, e.g., KH-40 available from Seimi Chemical Co., Ltd.The ratio of the surfactant in the composition (A) is usually 0.01 to 10parts by weight, and preferably 0.1 to 2 parts by weight, relative to100 parts by weight of the polymerizable compound.

The composition (A) may contain a solvent such as an organic solvent.Examples of the organic solvent may include a ketone such ascyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, and methylisobutyl ketone; an acetate ester such as butyl acetate and amylacetate; halogenated hydrocarbon such as chloroform, dichloromethane,and dichloroethane; an ether such as 1,4-dioxane, cyclopentyl methylether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolan, and1,2-dimethoxyethane; and aromatic hydrocarbon such as toluene, xylene,and mesitylene. The boiling point of the solvent is preferably 60 to250° C., and 60 to 150° C. from the viewpoint of excellenthandleability. The amount of the solvent to be used is usually 100 to1,000 parts by weight relative to 100 parts by weight of thepolymerizable compound.

The composition (A) may further contain an optional additive such as ametal, a metal complex, a dye, a pigment, a fluorescent material, aphosphorescent material, a leveling agent, a thixotropic agent, agelator, a polysaccharide, a ultraviolet absorber, an infrared absorber,an antioxidant, an ion exchange resin, and a metal oxide such astitanium oxide. The ratio of the optional additive in the polymerizablecomposition of the present invention is usually 0.1 to 20 parts byweight relative to 100 parts by weight of the polymerizable compound.

The composition (A) may be usually prepared by mixing the aforementionedcomponents.

[1.7. Method for Producing Optically Anisotropic Layer]

The optically anisotropic layer is a layer obtained by curing thecomposition (A).

Upon curing, a portion of the components in the composition (A) may bechemically changed, and may also be discharged to the outside of thesystem and disappear. For example, the all or most of the polymerizablecompound is usually polymerized during curing to form a polymer, and theall or most of the solvent is volatilized and disappears.

Curing of the composition (A) may be usually achieved as follows. Thecomposition (A) is applied onto a surface of a support or an orientationfilm formed on the support, the polymerizable liquid crystal compound inthe layer of the composition (A) is oriented in a desired direction, andif necessary, the layer of the composition (A) is dried. Then thepolymerizable compound is polymerized. The support and orientation filmused in this production process may be used as components of the phasedifference plate as they are. Alternatively, the support and theorientation film may be peeled off, and only the optically anisotropiclayer may be used as the phase difference plate.

The support is not particularly limited, and may be a plate or a filmformed from a known organic or inorganic material. Examples of theorganic material may include polycycloolefin [for example, ZEONEX,ZEONOR (registered trademark; available from ZEON CORPORATION), ARTON(registered trademark; available from JSR Corporation), and APEL(registered trademark; available from Mitsui Chemicals, Inc.)],polyethylene terephthalate, polycarbonate, polyimide, polyamide,polymethyl methacrylate, polystyrene, polyvinyl chloride,polytetrafluoroethylene, cellulose, cellulose triacetate, and polyethersulfone. Examples of the inorganic material may include silicon, glass,and calcite. In terms of cost and favorable handleability, the organicmaterial is preferable.

On the surface of the support, the orientation film may be formed. Inthis case, the optically anisotropic layer may be formed on theorientation film. With the orientation film, a liquid crystal compoundin the composition (A) may be oriented in one direction on the surface.

The orientation film contains, e.g., a polymer such as polyimide,polyvinyl alcohol, polyester, polyallylate, polyamideimide, andpolyetherimid. A solution containing such a polymer (composition fororientation film) may be applied onto a substrate to be in a film shape,dried, and subjected to a rubbing treatment in one direction, whereby,the orientation film can be obtained.

The thickness of the orientation film is preferably 0.001 to 5 μm, andmore preferably 0.001 to 1 μm.

The surface of the support or the orientation film may be subjected to arubbing treatment, if necessary. Such a rubbing treatment can impartorientation ability to the surface for orienting the compound that iscapable of exhibiting liquid crystallinity in the composition (A).

The method for rubbing treatment is not particularly limited, andexamples thereof may include a method in which the surface of thesupport or the orientation film is rubbed in a constant direction with aroll wrapped with cloth or felt formed of synthetic fibers such as nylonor natural fibers such as cotton. In order to remove powders (foreignsubstance) generated during the rubbing treatment to render the treatedsurface clean, it is preferable that the treated surface is cleanedafter the rubbing treatment with isopropyl alcohol or the like.

Other than the rubbing treatment method, a method of irradiating thesurface of the orientation film with polarized ultraviolet light canalso impart a function of restraining orientation of a cholestericliquid crystal layer having cholesteric regularity in one direction inthe surface to the orientation film.

In addition, an ion beam orientation method in which the support isirradiated obliquely with an ion beam such as Ar⁺ or the like to impartorientation performance to the support may be used.

Examples of the method for applying the composition (A) may include acurtain coating method, an extrusion coating method, a roll coatingmethod, a spin coating method, a dip coating method, a bar coatingmethod, a spray coating method, a slide coating method, a printingcoating method, a gravure coating method, a die coating method, a capcoating method, and a dipping method.

The layer of the composition (A) may be formed by such application, toorient the liquid crystal compound in the layer into a desired manner.The orientation may be immediately achieved by the application. Ifnecessary, the orientation may be achieved by subjecting the layer to anorientation treatment such as heating after the application.

In the layer of the composition (A) exhibiting orientation of desiredform, the main chain mesogen and the side chain mesogen of thepolymerizable liquid crystal compound with reverse wavelength dispersionare oriented in different directions. The angle between the orientationdirection of the main chain mesogen and the orientation direction of theside chain mesogen may be any angle that is not 0°, and preferably 70 to110° for achieving favorable reverse wavelength dispersion. Theorientation may be achieved by, e.g., appropriately selecting thecompound that forms desirable orientation as the polymerizable liquidcrystal compound with reverse wavelength dispersion from the compoundsin the aforementioned examples.

In the layer of the composition (A) formed by such application, it ispreferable that the mesogen of the polymerizable monomer is alsooriented in addition to the polymerizable liquid crystal compound withreverse wavelength dispersion. It is further preferable that the mesogenof the polymerizable monomer is oriented in parallel to any one of themain chain mesogen and the side chain mesogen of the polymerizableliquid crystal compound with reverse wavelength dispersion. When thepolymerizable monomer is oriented in such a form, favorable orientationcan be achieved, and reverse wavelength dispersion can be adjusted withprecision. Such orientation may be achieved by, e.g., appropriatelyselecting the compound that forms desirable orientation as thepolymerizable monomer from the compounds in the aforementioned examples.

Drying of the layer of the composition (A) may be achieved by a dryingmethod such as air drying, heated-air drying, drying under reducedpressure, and heated-air drying under reduced pressure. By the drying,the solvent can be removed.

As the method of polymerizing the polymerizable compound in the layer ofthe composition (A), a method that suits the nature of components of thecomposition (A) such as a polymerizable compound and a polymerizationinitiator may be appropriately selected. Examples thereof may include anactive energy ray irradiation method and a thermal polymerizationmethod. The active energy ray irradiation method is preferable since thereaction can proceed at room temperature without heating. Examples ofactive energy ray to be irradiated in this case may include light suchas visible light, ultraviolet light, and infrared light, and any energyray such as an electron beam. A method of irradiation with light such asultraviolet light is preferable because of simple operation. Thetemperature during irradiation of ultraviolet light is preferably 30° C.or lower. The lower limit of temperature during irradiation ofultraviolet light may be 15° C. or higher. The ultraviolet lightirradiation intensity usually falls within a range of 0.1 mW/cm² to1,000 mW/cm², and preferably 0.5 mW/cm² to 200 mW/cm².

[1.8. Optically Anisotropic Layer]

In the optically anisotropic layer, the main chain mesogen and the sidechain mesogen of the polymerizable liquid crystal compound with reversewavelength dispersion are oriented in different directions. The “mesogenof the polymerizable liquid crystal compound with reverse wavelengthdispersion” in the optically anisotropic layer is the mesogen thatexisted in the molecule of the polymerizable liquid crystal compoundwith reverse wavelength dispersion and is the mesogen in the polymerproduced by polymerization of the polymerizable liquid crystal compoundwith reverse wavelength dispersion. When the main chain mesogen and theside chain mesogen are oriented in different directions in this manner,the birefringence Δn of the optically anisotropic layer has reversewavelength dispersion property, and properties for favorable phasedifference plate can thereby be expressed.

The presence of reverse wavelength dispersion property of birefringenceΔn of the optically anisotropic layer may be confirmed by measurement ofbirefringence Δn at a variety of wavelengths λ with a phase differenceanalyzer (trade name “AxoScan” manufactured by Axometrics, Inc., etc.).

In addition to the mesogen of the polymerizable liquid crystal compoundwith reverse wavelength dispersion, it is preferable that the mesogen ofthe polymerizable monomer is also oriented in the optically anisotropiclayer. The “mesogen of the polymerizable monomer” in the opticallyanisotropic layer is a mesogen that existed in the molecule of thepolymerizable monomer and is the mesogen in the polymer produced bypolymerization of the polymerizable monomer.

It is preferable that the mesogen of the polymerizable monomer isoriented in parallel to any one of the main chain mesogen and the sidechain mesogen of the polymerizable liquid crystal compound with reversewavelength dispersion. When the polymerizable monomer is oriented insuch a form, favorable orientation can be achieved, and reversewavelength dispersion can be adjusted with precision. When thepolymerizable monomer has two or more mesogens per one molecule, one ofthe mesogens may be oriented in parallel to the main chain mesogen ofthe polymerizable liquid crystal compound with reverse wavelengthdispersion and the other may be oriented in parallel to the side chainmesogen of the polymerizable liquid crystal compound with reversewavelength dispersion.

In the phase difference plate of the present application, theretardation of the optically anisotropic layer satisfies the followingrelationship. Specifically, retardations Re0 (450 nm), Re0 (550 nm), andRe0 (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nm of a layerobtained by curing a composition (A0) and retardations Re (450 nm), Re(550 nm), and Re (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nmof an optically anisotropic layer satisfy relationship of the followingexpressions (i) and (ii) or relationship of the following expressions(iii) and (iv).Re0 (450 nm)/Re0 (550 nm)>Re (450 nm)/Re (550 nm)  Expression (i)Re0 (650 nm)/Re0 (550 nm)<Re (650 nm)/Re (550 nm)  Expression (ii)Re0 (450 nm)/Re0 (550 nm)<Re (450 nm)/Re (550 nm)  Expression (iii)Re0 (650 nm)/Re0 (550 nm)>Re (650 nm)/Re (550 nm)  Expression (iv)

The composition (A0) herein is a composition wherein the polymerizablemonomer in the composition (A) is replaced by a polymerizable liquidcrystal compound with reverse wavelength dispersion. For example, whenthe composition (A) contains a polymerizable liquid crystal compoundwith reverse wavelength dispersion, a polymerizable monomer, aphotopolymerization initiator, a surfactant, and a solvent and the ratioof total of the polymerizable liquid crystal compound with reversewavelength dispersion and the polymerizable monomer is x % by weight,the composition (A0) is a composition that contains a polymerizableliquid crystal compound with reverse wavelength dispersion, apolymerizable monomer, a photopolymerization initiator, a surfactant,and a solvent and in which the ratio of the polymerizable liquid crystalcompound with reverse wavelength dispersion is x % by weight and theratios of the photopolymerization initiator, the surfactant, and thesolvent are the same as those in the composition (A).

The conditions for formation of the layer obtained by curing thecomposition (A0) are the same as the conditions for formation of thelayer obtained by curing the composition (A). When the opticalproperties with respect to the layer obtained by curing the thusobtained composition (A0) satisfy the specific condition, the reversewavelength dispersion property can be controlled with precision.

The thickness of the optically anisotropic layer is not particularlylimited, and may be appropriately adjusted so that properties such asretardation fall within a desired range. Specifically, the lower limitof the thickness is preferably 0.1 μm or more, and more preferably 0.5μm or more, whereas the upper limit of the thickness is preferably 10 μmor less, and more preferably 5 μm or less.

[1.9. Phase Difference Plate: Other Components]

The phase difference plate of the present invention may solely consistof the optically anisotropic layer, or may have another layer, ifnecessary. For example, a member such as the support and the orientationfilm used in production of the optically anisotropic layer may remain asit is without being peeled off for use as the phase difference plate. Inthis case, the layer other than the optically anisotropic layer may beusually made as an optically isotropic layer. Examples of the optionallayer may include an adhesion layer for effecting adhesion of a layer toanother, a mat layer for improving the sliding property of the film, ahard-coat layer such as an impact-resistant polymethacrylate resinlayer, an anti-reflection layer, and an anti-fouling layer.

[2. Circularly Polarizing Plate]

The circularly polarizing plate of the present invention includes thephase difference plate of the present invention and a linear polarizer.

As the linear polarizer, a publicly known polarizer used in devices suchas a liquid crystal display device may be used. Examples of the linearpolarizer may include a linear polarizer obtained by adsorbing iodine ora dichroic dye to a polyvinyl alcohol film and then uniaxiallystretching the film in a boric acid bath, and a linear polarizerobtained by adsorbing iodine or a dichroic dye to a polyvinyl alcoholfilm, then stretching the film, and then further modifying one portionof polyvinyl alcohol unit in the molecular chain into a polyvinyleneunit. Other examples of the linear polarizer may include a polarizerhaving a function of separating polarized light into reflected light andtransmitted light, such as a grid polarizer, a multi-layer polarizer,and a cholesteric liquid crystal polarizer. Among these, a polarizercontaining polyvinyl alcohol is preferable.

When natural light is caused to be incident on the polarizer for use inthe present invention, only one type of polarized light is transmittedtherethrough. The degree of polarization of the polarizer for use in thepresent invention is not particularly limited, and is preferably 98% ormore, and more preferably 99% or more. The upper limit of the degree ofpolarization is ideally 100%. The average thickness of the polarizer ispreferably 5 to 80 μm.

When the phase difference plate of the present invention is used for thecircularly polarizing plate of the present invention, it is preferablethat the phase difference at a wavelength of 550 nm is 100 to 150 nm. Inthe circularly polarizing plate of the present invention, it ispreferable that the angle between a slow axis of the phase differenceplate and a transmission axis of the linear polarizer are 45° or near45°, specifically 40 to 50°. When the circularly polarizing plate hassuch a phase difference and angle, the circularly polarizing plate maybe usefully used for application as a component of a liquid crystaldisplay device, and the like.

The phase difference plate of the present invention may solely consistof the optically anisotropic layer, or may have an optional layer suchas a support and an orientation film in addition to the opticallyanisotropic layer. Therefore, the circularly polarizing plate of thepresent invention may similarly have any layer such as a support and anorientation film as an optional component.

[3. Image Display Device]

The image display device of the present invention has the phasedifference plate of the present invention. In the imaging display deviceof the present invention, the phase difference plate may be combinedwith a linear polarizer to be provided as a circularly polarizing plate.

Examples of the image display device of the present invention mayinclude a liquid crystal display device, an organic electroluminescentdisplay device, a plasma display device, a FED (field emission) displaydevice, and a SED (surface field emission) display device. The liquidcrystal display device is particularly preferable.

Examples of the driving mode of the liquid crystal cell may include anin-plane switching (IPS) mode, a vertical alignment (VA) mode, amulti-domain vertical alignment (MVA) mode, a continuous pinwheelalignment (CPA) mode, a hybrid alignment nematic (HAN) mode, a twistednematic (TN) mode, a super twisted nematic (STN) mode, and an opticalcompensated bend (OCB) mode. Among these, the in-plane switching modeand the vertical alignment mode are preferable, and the in-planeswitching mode is particularly preferable. A liquid crystal cell of thein-plane switching mode has a wide viewing angle. However, by applyingthe phase difference plate, the viewing angle can be further increased.

The image display device of the present invention may have only onesheet of the phase difference plate of the present invention or two ormore sheets thereof. In the image display device of the presentinvention, the phase difference plate of the present invention may beprovided by bonding the plate to another component such as a liquidcrystal cell via an adhesive.

EXAMPLES

The present invention will be specifically described hereinbelow withreference to Examples. However, the present invention is not limited tothe following Examples. The present invention may be implemented withany modifications without departing from the scope of the claims of thepresent invention and equivalents thereof.

Unless otherwise stated, “%” and “part” that represent an amount in thefollowing description are based on weight. Unless otherwise stated,operations described in the following were performed under conditions ofnormal temperature and normal pressure.

(Preparative Example 1) Synthesis of Compound (I)-1

Step 1: Synthesis of Intermediate Product A

20 g (144.8 mmol) of 2,5-dihydroxybenzaldehyde, 105.8 g (362.0 mmol) of4-(6-acryloyl-hex-1-yloxy) benzoic acid (available from DKSH), 5.3 g(43.4 mmol) of 4-(dimethylamino)pyridine, and 200 mL ofN-methylpyrrolidone were placed in a four-necked reaction vesselequipped with a thermometer under nitrogen flow, and a homogeneoussolution was produced. To the solution, 83.3 g (434.4 mmol) of1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (WSC) wasadded, and the mixture was stirred at 25° C. for 12 hours. Aftercompletion of the reaction, the reaction solution was added to 1.5 L ofwater, and the mixture was extracted with 500 mL of ethyl acetate. Theethyl acetate layer was dried over anhydrous sodium sulfate, and thesodium sulfate was removed by filtration. Ethyl acetate was distilledoff under reduced pressure from the filtrate with a rotary evaporator toobtain a pale yellow solid. The pale yellow solid was purified by silicagel column chromatography (toluene:ethyl acetate=9:1 (by volume)) toobtain 75 g of an intermediate product A as a white solid (yield:75.4%).

The structure thereof was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 10.20 (s, 1H), 8.18-8.12 (m, 4H),7.78 (d, 1H, J=2.8 Hz), 7.52 (dd, 1H, J=2.8 Hz, 8.7 Hz), 7.38 (d, 1H,J=8.7 Hz), 7.00-6.96 (m, 4H), 6.40 (dd, 2H, J=1.4 Hz, 17.4 Hz), 6.12(dd, 2H, J=10.6 Hz, 17.4 Hz), 5.82 (dd, 2H, J=1.4 Hz, 10.6 Hz), 4.18 (t,4H, J=6.4 Hz), 4.08-4.04 (m, 4H), 1.88-1.81 (m, 4H), 1.76-1.69 (m, 4H),1.58-1.42 (m, 8H)

Step 2: Synthesis of Compound (I)-1

10.5 g (15.3 mmol) of the intermediate product A synthesized in theprevious Step 1, 3.0 g (18.3 mmol) of 2-hydrazinobenzothiazole, and 80mL of tetrahydrofuran (THF) were placed in a 4-necked reaction vesselequipped with a thermometer under nitrogen flow, and a homogeneoussolution was produced. To the solution, 18 mg (0.08 mmol) of(±)-camphorsulfonic acid was added, and the mixture was stirred at 25°C. for 3 hours. After completion of the reaction, the reaction solutionwas added to 800 mL of 10% sodium bicarbonate water, and the mixture wasextracted with 100 mL of ethyl acetate twice. The ethyl acetate layerswere collected, and dried over anhydrous sodium sulfate, and the sodiumsulfate was removed by filtration. Ethyl acetate was distilled off underreduced pressure from the filtrate with a rotary evaporator to obtain apale yellow solid. The pale yellow solid was purified by silica gelcolumn chromatography (toluene:ethyl acetate=8:2 (by volume)) to obtain8.0 g of a compound (I)-1 as a pale yellow solid (yield: 62.7%). Thestructure of the target compound was identified by ¹H-NMR and massspectrum.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.30 (br, 1H), 8.19 (s, 1H),8.17-8.12 (m, 4H), 7.76 (d, 1H, J=3.0 Hz), 7.68 (d, 1H, J=7.5 Hz),7.45-7.39 (m, 3H), 7.28 (t, 1H, J=8.0 Hz), 7.18-7.14 (m, 4H), 7.09 (t,1H, J=8.0 Hz), 6.33 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd, 2H, J=10.5Hz, 17.5 Hz), 5.944 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.941 (dd, 1H, J=1.5Hz, 10.5 Hz), 4.14-4.10 (m, 8H), 1.80-1.75 (m, 4H), 1.69-1.63 (m, 4H),1.53-1.38 (m, 8H) LCMS(APCI): calcd for C₄₆H₄₇N₃O₁₀S: 833 [M⁺]. Found:833.

<Measurement of Phase Transition Temperature>

10 mg of the compound (I)-1 was weighted, and placed between two glasssubstrates with a polyimide orientation film that had been subjected toa rubbing treatment while the compound (I)-1 was in a solid state. Thesubstrates was placed on a hot plate, and the temperature was increasedfrom 50° C. to 200° C., and then decreased to 50° C. A histologicalchange during the increase and decrease in the temperature was observedwith a polarizing microscope (ECLIPSE LV100POL manufactured by NikonCorporation). As a result, during the increase in the temperature, asolid phase was transformed into a nematic liquid crystal phase at 102°C., and then into an isotropic liquid phase at 165° C. In contrast,during the decrease in the temperature, the isotropic liquid phase wastransformed into a nematic liquid crystal phase at 140° C., and theninto a solid phase at 50° C. or lower.

Comparative Example 1 C1-1. Preparation of Composition (A0)

A mixture of a composition shown in the following Table 1 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A0).

TABLE 1 Polymerizable liquid crystal 19.3 Parts compound with reversewavelength dispersion (I)-1 (Prepared in Preparative Example 1)Photopolymerization initiator:  0.6 Parts Irgacure-379 (Produced by BASFJapan Ltd.) Surfactant: Ftergent 209F 1%  5.8 Parts solution (NeosCompany Limited) Cyclopentanone 74.2 Parts

C1-2. Production of Phase Difference Plate

One surface of a support (ZEONOR Film, trade name “ZF16”, available fromZEON CORPORATION) was subjected to an orientation treatment by rubbing.The composition (A0) obtained in Step (C1-1) was applied onto thesurface with a spin coater so that the dried film thickness was 1.4 μm.The support was heated at 130° C. for 2 minutes to dry the layer of thecomposition (A0). A multiple-layered product including the support andthe dried layer of the composition (A0) formed on the support wasthereby obtained.

Subsequently, the multiple-layered product was irradiated withultraviolet light using a metal halide lamp to polymerize thepolymerizable liquid crystal compound. In the irradiation dose ofultraviolet light, an illuminance was 16 mW/cm², and an light exposuredose was 100 mJ/cm². A phase difference plate including the support andan optically anisotropic layer with a film thickness of 1.4 m formed onthe support was thereby obtained.

C1-3. Measurement of Wavelength Dispersion

For the phase difference plate produced in Step (C1-2), a birefringenceΔn was measured at a variety of wavelengths λ with a phase differenceanalyzer (trade name: AxoScan) manufactured by Axometrics, Inc., andwavelength dispersion property of Δn was determined. The measuredwavelength dispersion property is shown in FIG. 1.

From the measurement results, Re0 (450 nm)/Re0 (550 nm)=0.918 and Re0(650 nm)/Re0 (550 nm)=0.982.

C1-4. Measurement of Refractive Index Wavelength Dispersion

For the phase difference plate produced in Step (C1-2), the refractiveindex was measured with a refractive index meter: prism couplermanufactured by Metricon Corporation. The refractive index was measuredat wavelengths λ of 407 nm, 532 nm, and 633 nm, and the measured valuesat the three wavelengths were fit to a Cauchy model. The results areshown in FIG. 2. The refractive index in a fast axis direction had lowervalues and larger wavelength dispersion as compared with the refractiveindex in a slow axis direction. This shows that the phase differenceplate exhibits reverse wavelength dispersion property.

Reference Example 1

The phase difference plate obtained in Step (C1-2) of ComparativeExample 1 was irradiated with polarized ultraviolet light, and theabsorption spectrum was measured. In the measurement, aspectrophotometer (main instrument trade name “V7200”, light receptionportion trade name “VAR7020” manufactured by JASCO Corporation) wasused.

As a result, two absorption peaks at 266 nm and 347 nm were observed.When the polarization direction was rotated, the height of the peaks waschanged. When the rubbing direction was set to 0° among a variety ofdirections in parallel to the surface of the phase difference plate, theazimuth angle of polarization in which the absorption at 347 nm reachedthe maximum was 90°. The relationship between the azimuth angle ofpolarization and the measured absorption is shown in FIG. 3.

The wavelength dispersion of refractive index of a compound having astructure similar to the main chain mesogen of the compound (I)-1 and acompound having a structure similar to the side chain mesogen of thecompound (I)-1 in the visible light region was examined. The wavelengthdispersion of the latter was larger. In general, a compound having alarge visible light wavelength dispersion tends to have an absorptionpeak close to the visible light region. Further, when the polarizationdirection is generally parallel to the long axis direction, theabsorption peak reaches the maximum. Therefore, attribution wasdetermined that the peak at 266 nm was derived from the main chainmesogen, and the peak at 347 nm was derived from the side chain mesogen.In addition, this shows that the orientation direction of the main chainmesogen is orthogonal to the orientation direction of the side chainmesogen.

Example 1 1-1. Preparation of Composition (A)

A mixture of a composition shown in the following Table 2 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A-1).

TABLE 2 Polymerizable liquid crystal 17.4 Parts  compound with reversewavelength dispersion (I)-1 (Prepared in Preparative Example 1)Polymerizable monomer (II)-1 1.9 Parts (Compound represented by thefollowing formula (II)-1) Photopolymerization initiator: 0.6 PartsIrgacure-379 (Produced by BASF Japan Ltd.) Surfactant: Ftergent 209F 1%5.8 Parts solution (Neos Company Limited) Cyclopentanone 74.2 Parts 

Separately from the composition (A-1), a composition was prepared byadding 20.0% by weight of a polymerizable monomer (II)-1 tocyclopentanone. The composition was applied onto a substrate having beensubjected to an orientation treatment, and a solvent was dried once.After that, the temperature was changed in a range of room temperatureto 200° C., and the presence or absence of liquid crystallinity wasobserved with a polarizing microscope. Liquid crystallinity was observedat 122° C.

1-2. Production and Evaluation of Phase Difference Plate

A phase difference plate was produced in the same manner as in Step(C1-2) of Comparative Example 1 except that the composition (A-1)obtained in Step (1-1) was used in place of the composition (A0)obtained in Step (C1-1). The film thickness of the optically anisotropiclayer of the phase difference plate thus obtained was 1.2 μm.

For the phase difference plate thus obtained, the birefringence Δn wasmeasured at a variety of wavelengths λ in the same manner as in Step(C1-3) of Comparative Example 1, whereby the wavelength dispersionproperty of Δn was determined. The measured wavelength dispersionproperty is shown in FIG. 4 in comparison with the results ofComparative Example 1.

From the measurement results, Re (450 nm)/Re (550 nm)=0.99, and Re (650nm)/Re (550 nm)=0.97, which showed that the reverse dispersibilitybecame smaller as compared with Comparative Example 1.

For the phase difference plate thus obtained, the refractive index wasmeasured in the same manner as in Step (C1-4) of Comparative Example 1.The measured values at three wavelengths were fit to a Cauchy model. Theresults are shown in FIG. 5 in comparison with the results ofComparative Example 1. The wavelength dispersion of refractive index inthe slow axis direction was not largely different from that inComparative Example 1, but the wavelength dispersion of refractive indexin the fast axis direction became smaller as compared with ComparativeExample 1. Therefore, the reverse wavelength dispersion property of Δnof the phase difference plate became small.

Example 2 2-1. Preparation of Composition (A-2)

A mixture of a composition shown in the following Table 3 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A-2).

TABLE 3 Polymerizable liquid crystal 17.4 Parts  compound with reversewavelength dispersion (I)-1 (Prepared in Preparative Example 1)Polymerizable monomer (IV) 1.9 Parts (Compound represented by thefollowing formula (IV)) Photopolymerization initiator: 0.6 PartsIrgacure-379 (Produced by BASF Japan Ltd.) Surfactant: Ftergent 209F 1%5.8 Parts solution (Neos Company Limited) Cyclopentanone 74.2 Parts 

Separately from the composition (A-2), a composition was prepared byadding 20.0% by weight of a polymerizable monomer (IV) tocyclopentanone. The composition was applied onto a substrate having beensubjected to an orientation treatment, and a solvent was dried once.After that, the temperature was changed in a range of room temperatureto 200° C., and the presence or absence of liquid crystallinity wasobserved with a polarizing microscope. It showed non-liquidcrystallinity.

2-2. Production and Evaluation of Phase Difference Plate

A phase difference plate was produced in the same manner as in Step(C1-2) of Comparative Example 1 except that the composition (A-2)obtained in Step (2-1) was used in place of the composition (A0)obtained in Step (C1-1). The film thickness of the optically anisotropiclayer of the phase difference plate thus obtained was 1.5 μm.

For the phase difference plate thus obtained, the birefringence Δn wasmeasured at a variety of wavelengths λ in the same manner as in Step(C1-3) of Comparative Example 1, whereby the wavelength dispersionproperty of Δn was determined. The measured wavelength dispersionproperty is shown in FIG. 6 in comparison with the results ofComparative Example 1.

From the measurement results, Re (450 nm)/Re (550 nm)=0.963, and Re (650nm)/Re (550 nm)=0.979, which showed that the reverse dispersibilitybecame smaller as compared with Comparative Example 1.

For the phase difference plate thus obtained, the refractive index wasmeasured in the same manner as in Step (C1-4) of Comparative Example 1.The measured values at three wavelengths were fit to a Cauchy model. Theresults are shown in FIG. 7 in comparison with the results ofComparative Example 1. The wavelength dispersion of refractive index inthe slow axis direction became larger than that in Comparative Example1, and the wavelength dispersion of refractive index in the fast axisdirection was not largely changed as compared with ComparativeExample 1. Therefore, the reverse wavelength dispersion property of Δnof the phase difference plate became small.

Example 3 3-1. Preparation of Composition (A-3)

A mixture of a composition shown in the following Table 4 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A-3).

TABLE 4 Polymerizable liquid crystal 17.4 Parts  compound with reversewavelength dispersion (I)-1 (Prepared in Preparative Example 1)Polymerizable monomer (III)-4 1.9 Parts (Compound represented by thefollowing formula (III)-4) Photopolymerization initiator: 0.6 PartsIrgacure-379 (Produced by BASF Japan Ltd.) Surfactant: Ftergent 209F 1%5.8 Parts solution (Neos Company Limited) Cyclopentanone 74.2 Parts 

Separately from the composition (A-3), a composition was prepared byadding 20.0% by weight of a polymerizable monomer (III)-4 tocyclopentanone. The composition was applied onto a substrate having beensubjected to an orientation treatment, and a solvent was dried once.After that, the temperature was changed in a range of room temperatureto 200° C., and the presence or absence of liquid crystallinity wasobserved with a polarizing microscope. It showed non-liquidcrystallinity.

3-2. Production and Evaluation of Phase Difference Plate

A phase difference plate was produced in the same manner as in Step(C1-2) of Comparative Example 1 except that the composition (A-3)obtained in Step (3-1) was used in place of the composition (A0)obtained in Step (C1-1). The film thickness of the optically anisotropiclayer of the phase difference plate thus obtained was 1.3 μm.

For the phase difference plate thus obtained, the birefringence Δn wasmeasured at a variety of wavelengths λ in the same manner as in Step(C1-3) of Comparative Example 1, whereby the wavelength dispersionproperty of Δn was determined. The measured wavelength dispersionproperty is shown in FIG. 8 in comparison with the results ofComparative Example 1.

From the measurement results, Re (450 nm)/Re (550 nm)=0.969, and Re (650nm)/Re (550 nm)=0.980, which showed that the reverse dispersibilitybecame smaller as compared with Comparative Example 1.

For the phase difference plate thus obtained, the refractive index wasmeasured in the same manner as in Step (C1-4) of Comparative Example 1.The measured values at three wavelengths were fit to a Cauchy model. Theresults are shown in FIG. 9 in comparison with the results ofComparative Example 1. The wavelength dispersion of refractive index inthe slow axis direction was not largely different from that inComparative Example 1, but the wavelength dispersion of refractive indexin the fast axis direction became smaller as compared with ComparativeExample 1. Therefore, the reverse wavelength dispersion property of Δnof the phase difference plate became small.

Example 4 4-1. Preparation of Composition (A-4)

A mixture of a composition shown in the following Table 5 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A-4).

TABLE 5 Polymerizable liquid crystal 9.7 Parts compound with reversewavelength dispersion (I)-1 (Prepared in Preparative Example 1)Polymerizable monomer (III)-1 9.6 Parts (Compound represented by thefollowing formula (III)-1) Photopolymerization initiator: 0.6 PartsIrgacure-379 (Produced by BASF Japan Ltd.) Surfactant: Ftergent 209F 1%5.8 Parts solution (Neos Company Limited) Cyclopentanone 74.2 Parts 

Separately from the composition (A-4), a composition was prepared byadding 20.0% by weight of a polymerizable monomer (III)-1 tocyclopentanone. The composition was applied onto a substrate having beensubjected to an orientation treatment, and a solvent was dried once.After that, the temperature was changed in a range of room temperatureto 200° C., and the presence or absence of liquid crystallinity wasobserved with a polarizing microscope. It showed non-liquidcrystallinity.

4-2. Production and Evaluation of Phase Difference Plate

A phase difference plate was produced in the same manner as in Step(C1-2) of Comparative Example 1 except that the composition (A-4)obtained in Step (4-1) was used in place of the composition (A0)obtained in Step (C1-1). The film thickness of the optically anisotropiclayer of the phase difference plate thus obtained was 1.7 μm.

For the phase difference plate thus obtained, the birefringence Δn wasmeasured at a variety of wavelengths λ in the same manner as in Step(C1-3) of Comparative Example 1, whereby the wavelength dispersionproperty of Δn was determined. The measured wavelength dispersionproperty is shown in FIG. 10 in comparison with the results ofComparative Example 1.

From the measurement results, Re (450 nm)/Re (550 nm)=0.761, and Re (650nm)/Re (550 nm)=1.019, which showed that the reverse dispersibilitybecame larger as compared with Comparative Example 1.

For the phase difference plate thus obtained, the refractive index wasmeasured in the same manner as in Step (C1-4) of Comparative Example 1.The measured values at three wavelengths were fit to a Cauchy model. Theresults are shown in FIG. 11 in comparison with the results ofComparative Example 1. The wavelength dispersion of refractive index inthe slow axis direction was not largely different from that inComparative Example 1, but the wavelength dispersion of refractive indexin the fast axis direction became larger as compared with ComparativeExample 1. Therefore, the reverse wavelength dispersion property of Δnof the phase difference plate became large.

Example 5 5-1. Preparation of Composition (A-5)

A mixture of a composition shown in the following Table 6 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A-5).

TABLE 6 Polymerizable liquid crystal 17.4 Parts  compound with reversewavelength dispersion (I)-1 (Prepared in Preparative Example 1)Polymerizable monomer (III)-2 1.9 Parts (Compound represented by thefollowing formula (III)-2) Photopolymerization initiator: 0.6 PartsIrgacure-379 (Produced by BASF Japan Ltd.) Surfactant: Ftergent 209F 1%5.8 Parts solution (Neos Company Limited) Cyclopentanone 74.2 Parts 

Separately from the composition (A-5), a composition was prepared byadding 20.0% by weight of a polymerizable monomer (III)-2 tocyclopentanone. The composition was applied onto a substrate having beensubjected to an orientation treatment, and a solvent was dried once.After that, the temperature was changed in a range of room temperatureto 200° C., and the presence or absence of liquid crystallinity wasobserved with a polarizing microscope. It showed non-liquidcrystallinity.

5-2. Production and Evaluation of Phase Difference Plate

A phase difference plate was produced in the same manner as in Step(C1-2) of Comparative Example 1 except that the composition (A-5)obtained in Step (5-1) was used in place of the composition (A0)obtained in Step (C1-1). The film thickness of the optically anisotropiclayer of the phase difference plate thus obtained was 1.3 μm.

For the phase difference plate thus obtained, the birefringence Δn wasmeasured at a variety of wavelengths λ in the same manner as in Step(C1-3) of Comparative Example 1, whereby the wavelength dispersionproperty of Δn was determined. The measured wavelength dispersionproperty is shown in FIG. 12 in comparison with the results ofComparative Example 1.

From the measurement results, Re (450 nm)/Re (550 nm)=0.916, and Re (650nm)/Re (550 nm)=1.010, which showed that the reverse dispersibilitybecame larger as compared with Comparative Example 1.

For the phase difference plate thus obtained, the refractive index wasmeasured in the same manner as in Step (C1-4) of Comparative Example 1.The measured values at three wavelengths were fit to a Cauchy model. Theresults are shown in FIG. 13 in comparison with the results ofComparative Example 1. The wavelength dispersion of refractive index inthe slow axis direction was not largely different from that inComparative Example 1, but the wavelength dispersion of refractive indexin the fast axis direction became larger as compared with ComparativeExample 1. Therefore, the reverse wavelength dispersion property of Δnof the phase difference plate became large.

(Preparative Example 2) Synthesis of Compound 25

Step 1: Synthesis of Intermediate Product H1

7.28 g (66.1 mmol) of hydroquinone, 2.38 g (59.5 mmol) of sodiumhydroxide, and 50 mL of distilled water were placed in a 3-neckedreaction vessel equipped with a thermometer under nitrogen flow. To thesolution, 9.90 g (60.1 mmol) of 8-chloro-1-n-octanol was added dropwiseover 30 minutes. After completion of dropwise addition, the entirevolume was refluxed for 5 hours. After completion of the reaction, thereaction solution was cooled to 25° C., to deposit a white solid, andthe white solid was collected by filtration. The resulting solid wasrecrystallized using 120 mL of toluene to obtain 7.93 g of anintermediate product H1 as a white solid (yield: 56.1%).

The structure of the target compound was identified by 1H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.86 (s, 1H), 6.72 (dd, 2H, J=2.5Hz, 8.0 Hz), 6.65 (dd, 2H, J=2.5 Hz, 8.0 Hz), 4.33 (t, 1H, J=5.0 Hz),3.82 (t, 2H, J=6.5 Hz), 3.37 (dt, 2H, J=5.0 Hz, 6.5 Hz), 1.65 (tt, 2H,J=6.5 Hz, 6.5 Hz), 1.28-1.42 (m, 10H)

Step 2: Synthesis of Intermediate Product I1

7.84 g (32.9 mmol) of the intermediate product H1 synthesized in Step 1,2.61 g (36.2 mmol) of acrylic acid, 40.8 mg (0.329 mmol) of4-methoxyphenol, 316 mg (3.29 mmol) of methanesulfonic acid, and 40 mLof toluene were placed in a 3-necked reaction vessel equipped with athermometer under nitrogen flow, and the entire volume was refluxed for6 hours. The reaction solution was cooled to 25° C., 200 mL of water wasadded, and the mixture was extracted with 100 mL of ethyl acetate. Theethyl acetate layer was dried over anhydrous sodium sulfate, and thesodium sulfate was removed by filtration. Ethyl acetate was distilledoff under reduced pressure from the filtrate with a rotary evaporator toobtain a brown solid. The brown solid was purified by silica gel columnchromatography (toluene:THF=95:5) to obtain 6.95 g of an intermediateproduct I1 as a white solid (yield: 71.9%).

The structure of the target compound was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.86 (s, 1H), 6.72 (dd, 2H, J=2.5Hz, 9.0 Hz), 6.65 (dd, 2H, J=2.5 Hz, 8.0 Hz), 6.31 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.17 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz,10.5 Hz), 4.10 (t, 2H, J=6.5 Hz), 3.83 (t, 2H, J=6.5 Hz), 1.58-1.68 (m,4H), 1.30-1.39 (m, 8H)

Step 3: Synthesis of Intermediate Product J1

6.86 g (39.8 mmol) of trans-1,4-cyclohexanedicarboxylic acid, 70 mL ofTHF, and 14 mL of DMF were placed in a 3-necked reaction vessel equippedwith a thermometer under nitrogen flow. To the mixture, 2.28 g (19.9mmol) of methanesufonyl chloride was added, and the reaction vessel wasplaced in a water bath to adjust the inner temperature of the reactionsolution to 20° C. Subsequently, 2.20 g (21.7 mmol) of triethylamine wasadded dropwise over 5 minutes while the inner temperature of thereaction solution was maintained at 20 to 30° C. After completion ofdropwise addition, the entire volume was further stirred at 25° C. for 2hours. To the obtained reaction mixture, 221 mg (1.81 mmol) of4-(dimethylamino)pyridine and 5.30 g (18.1 mmol) of the intermediateproduct I1 synthesized in the aforementioned Step 2 were added, and thereaction vessel was placed in a water bath again to adjust the innertemperature of the reaction solution to 15° C. Further, 2.20 g (21.7mmol) of triethylamine was added dropwise over 5 minutes while the innertemperature of the reaction solution was maintained at 20 to 30° C.After completion of dropwise addition, the entire volume was furtherstirred at 25° C. for 2 hours. After completion of the reaction, 300 mLof distilled water and 100 mL of saturated saline solution were added tothe reaction solution, and the mixture was extracted with 100 mL ofethyl acetate twice. The organic layer was dried over anhydrous sodiumsulfate, and the sodium sulfate was removed by filtration. The filtratewas concentrated with a rotary evaporator. The concentrate was thenpurified by silica gel column chromatography (toluene:THF=85:15) toobtain 5.23 g of an intermediate product J1 as a white solid (yield:64.6%).

The structure of the target compound was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.1 (s, 1H), 6.98 (dd, 2H, J=2.5Hz, 9.0 Hz), 6.92 (dd, 2H, J=2.5 Hz, 8.0 Hz), 6.31 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.17 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.92 (dd, 1H, J=1.5 Hz,10.5 Hz), 4.10 (t, 2H, J=6.5 Hz), 3.93 (t, 2H, J=6.5 Hz), 2.19-2.25 (m,1H), 2.04-2.10 (m, 2H), 1.94-1.98 (m, 2H), 1.69 (tt, 2H, J=6.5 Hz, 6.5Hz), 1.57-1.64 (m, 2H), 1.31-1.52 (m, 13H)

Step 4: Synthesis of Intermediate Product K1

4.00 g (8.96 mmol) of the intermediate product J1 synthesized in theaforementioned Step 3 was dissolved in 60 mL of THF in a 3-neckedreaction vessel equipped with a thermometer under nitrogen flow. To thesolution, 1.07 g (9.32 mmol) of methanesufonyl chloride was added, andthe reaction vessel was placed in a water bath to adjust the innertemperature of the reaction solution to 20° C. To the reaction solution,944 mg (9.32 mmol) of triethylamine was added dropwise over 5 minuteswhile the inner temperature of the reaction solution was maintained at20 to 30° C. The entire volume was stirred at 25° C. for 2 hours. To thereaction mixture, 92.0 mg (0.748 mmol) of 4-(dimethylamino)pyridine and548 mg (3.97 mmol) of 2,5-dihydroxybenzaldehyde were added, and thereaction vessel was placed in a water bath again to adjust the innertemperature of the reaction solution to 15° C. 944 mg (9.32 mmol) oftriethylamine was added dropwise over 5 minutes while the innertemperature of the reaction solution was maintained at 20 to 30° C.After completion of dropwise addition, the entire volume was furtherstirred at 25° C. for 2 hours. After completion of the reaction, 350 mLof distilled water and 50 mL of saturated saline solution were added tothe reaction solution, and the mixture was extracted with 150 mL ofchloroform twice. The organic layer was dried over anhydrous sodiumsulfate, and the sodium sulfate was removed by filtration. The filtratewas concentrated with a rotary evaporator. The concentrate was dissolvedin 15 mL of THF. To the solution, 200 mL of methanol was added todeposit a crystal, and the deposited crystal was collected byfiltration. The resulting crystal was washed with methanol, and dried invacuo to obtain 2.85 g of an intermediate product K1 as a white solid(yield: 72.3%).

The structure of the target compound was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.1 (s, 1H), 7.61 (d, 1H, J=2.5Hz), 7.37 (dd, 1H, J=2.5 Hz, 8.5 Hz), 7.20 (d, 1H, J=8.5 Hz), 6.97 (dd,4H, J=2.0 Hz, 9.0 Hz), 6.88 (dd, 4H, J=2.0 Hz, 9.0 Hz), 6.40 (dd, 2H,J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H,J=1.5 Hz, 10.5 Hz), 4.16 (t, 4H, J=6.5 Hz), 3.93 (t, 4H, J=6.5 Hz),2.57-2.74 (m, 4H), 2.26-2.37 (m, 8H), 1.65-1.80 (m, 16H), 1.35-1.48 (m,16H)

Step 5: Synthesis of Intermediate Product J

2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole and 20 mL of DMF wereplaced in a 4-necked reaction vessel equipped with a thermometer undernitrogen flow, and a homogeneous solution was produced. To the solution,8.36 g of (60.5 mmol) of potassium carbonate and 3.08 g (14.5 mmol) of1-iodohexane were added, and the entire volume was stirred at 50° C. for7 hours. After completion of the reaction, the reaction solution wascooled to 20° C., 200 mL of water was added to the reaction solution,and the mixture was extracted with 300 mL of ethyl acetate. The ethylacetate layer was dried over anhydrous sodium sulfate, and the sodiumsulfate was removed by filtration. Ethyl acetate was distilled off underreduced pressure from the filtrate with a rotary evaporator to obtain ayellow solid. The yellow solid was purified by silica gel columnchromatography (hexane:ethyl acetate=75:25) to obtain 2.10 g of anintermediate product J as a white solid (yield: 69.6%).

The structure of the target compound was identified by 1H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.53 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 8.0 Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0 Hz, 8.0 Hz, 8.0 Hz), 4.22 (s, 2H), 3.74 (t,2H, J=7.5 Hz), 1.69-1.76 (m, 2H), 1.29-1.42 (m, 6H), 0.89 (t, 3H, J=7.0Hz)

Step 6: Synthesis of Compound 25

1.95 g (1.96 mmol) of the intermediate product K1 synthesized in theaforementioned Step 4, 441 mg (1.76 mmol) of the intermediate product Jsynthesized in the aforementioned Step 5, 45.6 mg (0.196 mmol) of(±)-10-camphorsulfonic acid, 24 mL of THF, and 6 mL of ethanol wereplaced in a 3-necked reaction vessel equipped with a thermometer undernitrogen flow, and a homogeneous solution was produced. After that, theentire volume was stirred at 40° C. for 5 hours. After completion of thereaction, the reaction solution was added to 100 mL of water, and themixture was extracted with 200 mL of chloroform. The chloroform layerwas dried over anhydrous sodium sulfate, and the sodium sulfate wasremoved by filtration. Chloroform was distilled off under reducedpressure from the filtrate with a rotary evaporator to obtain a yellowsolid. The yellow solid was purified by silica gel column chromatography(toluene:ethyl acetate=95:5) to obtain 1.56 g of a compound 25 as a paleyellow solid (yield: 64.9%).

The structure of the target compound was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (d, 1H, J=1.5 Hz), 7.66-7.70(m, 3H), 7.34 (dd, 1H, J=1.5 Hz, 7.8 Hz), 7.09-7.18 (m, 3H), 6.96-7.00(m, 4H), 6.86-6.90 (m, 4H), 6.41 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd,2H, J=10.5 Hz, 17.5 Hz), 5.81 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.30 (t, 2H,J=7.5 Hz), 4.16 (t, 4H, J=6.5 Hz), 3.94 (t, 4H, J=6.5 Hz), 2.56-2.72 (m,4H), 2.27-2.38 (m, 8H), 1.65-1.81 (m, 18H), 1.32-1.49 (m, 22H), 0.90 (t,3H, J=7.5 Hz)

Comparative Example 2 C2-1. Preparation of Composition (A0-1)

A mixture of a composition shown in the following Table 7 was stirredhomogeneously, and filtered through a 0.6-μm filter, to obtain acomposition (A0-1).

TABLE 7 Polymerizable liquid crystal 19.4 Parts compound with reversewavelength dispersion 25 (Prepared in Preparative Example 2)Photopolymerization initiator:  0.6 Parts Irgacure-379 (Produced by BASFJapan Ltd.) Surfactant: Ftergent 209F 1%  5.8 Parts solution (NeosCompany Limited) Cyclopentanone 74.2 Parts

C2-2. Production of Phase Difference Plate

A multiple-layered product including a layer of the composition (A0-1)was obtained in the same manner as in (C1-2) of Comparative Example 1except that the composition (A0-1) was used in place of the composition(A0). Further, a phase difference plate including a support and anoptically anisotropic layer with a film thickness of 1.5 μm formed onthe support was obtained.

C2-3. Measurement of Wavelength Dispersion

For the phase difference plate produced in Step (C2-2), thebirefringence Δn was measured at a variety of wavelengths λ in the samemanner as in Step (C1-3) of Comparative Example 1, and the wavelengthdispersion property of Δn was determined. The measured wavelengthdispersion property is shown in FIG. 14.

From the measurement results, Re0 (450 nm)/Re0 (550 nm)=0.824 and Re0(650 nm)/Re0 (550 nm)=1.031.

C2-4. Measurement of Refractive Index Wavelength Dispersion

For the phase difference plate produced in Step (C2-2), the refractiveindex was measured in the same manner as in Step (C1-4) of ComparativeExample 1. The refractive index was measured at wavelengths λ of 407 nm,532 nm, and 633 nm, and the measured values at the three wavelengthswere fit to a Cauchy model. The results are shown in FIG. 15. In FIG.15, a dashed line shows a refractive index in a fast axis direction, anda solid line shows a refractive index in a slow axis direction. Therefractive index in the fast axis direction had lower values and largerwavelength dispersion as compared with the refractive index in the slowaxis direction. This shows that the phase difference plate exhibitsreverse wavelength dispersion property.

Example 6 6-1. Preparation of Composition (A-6)

A mixture of a composition shown in the following Table 8 was stirredhomogeneously, and filtered through a 0.6-μm 0.6 m filter, to obtain acomposition (A-6).

TABLE 8 Polymerizable liquid crystal 17.8 Parts  compound with reversewavelength dispersion 25 (Prepared in Preparative Example 2)Polymerizable monomer (IV) 2.2 Parts (Compound represented by theformula (IV) above) Photopolymerization initiator: 0.6 PartsIrgacure-379 (Produced by BASF Japan Ltd.) Surfactant: Ftergent 209F 1%5.8 Parts solution (Neos Company Limited) Cyclopentanone 73.6 Parts 

Separately from the composition (A-6), a composition was prepared byadding 20.0% by weight of a polymerizable monomer (IV) tocyclopentanone. The composition was applied onto a substrate having beensubjected to an orientation treatment, and a solvent was dried once.After that, the temperature was changed in a range of room temperatureto 200° C., and the presence or absence of liquid crystallinity wasobserved with a polarizing microscope. It showed non-liquidcrystallinity.

6-2. Production and Evaluation of Phase Difference Plate

A phase difference plate was produced in the same manner as in Step(C2-2) of Comparative Example 2 except that the composition (A-6)obtained in Step (6-1) was used in place of the composition (A0-1)obtained in Step (C2-1). The film thickness of the optically anisotropiclayer of the phase difference plate thus obtained was 1.3 μm.

For the phase difference plate thus obtained, the birefringence Δn wasmeasured at a variety of wavelengths λ in the same manner as in Step(C2-3) of Comparative Example 2, whereby the wavelength dispersionproperty of Δn was determined. The measured wavelength dispersionproperty is shown in FIG. 16 in comparison with the results ofComparative Example 2. In FIG. 16, the results of Example 6 are shown bya solid line while the results of Comparative Example 2 are shown by adashed line.

From the measurement results, Re (450 nm)/Re (550 nm)=0.918, and Re (650nm)/Re (550 nm)=0.982, which showed that the reverse dispersibilitybecame smaller as compared with Comparative Example 2.

For the phase difference plate thus obtained, the refractive index wasmeasured in the same manner as in Step (C2-4) of Comparative Example 2.The measured values at three wavelengths were fit to a Cauchy model. Theresults are shown in FIG. 17 in comparison with the results ofComparative Example 2. In FIG. 17, the results of Example 6 are shown bya solid line while the results of Comparative Example 2 are shown by adashed line. The wavelength dispersion of refractive index in the slowaxis direction became smaller than that in Comparative Example 2, andthe wavelength dispersion of refractive index in the fast axis directionbecame smaller as compared with Comparative Example 2. Therefore, thereverse wavelength dispersion property of Δn of the phase differenceplate became large.

The invention claimed is:
 1. A phase difference plate comprising an optically anisotropic layer obtained by curing a composition (A) containing a polymerizable liquid crystal compound with reverse wavelength dispersion and a polymerizable monomer, wherein: the polymerizable liquid crystal compound with reverse wavelength dispersion has a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in the molecule thereof; the main chain mesogen and the side chain mesogen of the polymerizable liquid crystal compound with reverse wavelength dispersion are oriented in different directions in the optically anisotropic layer, whereby a birefringence Δn of the optically anisotropic layer has reverse wavelength dispersion property; and retardations Re0 (450 nm), Re0 (550 nm), and Re0 (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nm of a layer obtained by curing a composition (A0) in which the polymerizable monomer in the composition (A) was replaced by the polymerizable liquid crystal compound with reverse wavelength dispersion and retardations Re (450 nm), Re (550 nm), and Re (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nm of the optically anisotropic layer satisfy relationship of the following expressions (iii) and (iv): Re0 (450 nm)/Re0 (550 nm)<Re (450 nm)/Re (550 nm)  Expression (iii) Re0 (650 nm)/Re0 (550 nm)>Re (650 nm)/Re (550 nm)  Expression (iv).
 2. The phase difference plate according to claim 1, wherein the polymerizable liquid crystal compound with reverse wavelength dispersion is a compound represented by the following formula (I):

[in the formula, Y¹ to Y⁶ are each independently a chemical single bond, —O—, —S—, O— C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; G¹ and G² are each independently a divalent aliphatic group having 1 to 20 carbon atoms and optionally having a substituent [the aliphatic group may have one or more of —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)— inserted thereinto per one aliphatic group, provided that a case where two or more —O— groups or —S— groups are adjacently inserted is excluded, wherein R² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms]; Z¹ and Z² are each independently an alkenyl group having 2 to 10 carbon atoms that may be substituted by a halogen atom; A^(x) is an organic group of 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; A^(y) is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 12 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 12 carbon atoms and optionally having a substituent, —C(═O)—R³, —SO₂—R⁶, or an organic group of 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, wherein the aromatic ring of A^(x) and A^(y) may have a substituent, and A^(x) and A^(y) may together form a ring, and wherein R³ is an alkyl group having 1 to 12 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 12 carbon atoms and optionally having a substituent, and a cycloalkyl group having 3 to 12 carbon atoms and optionally having a substituent, and R⁶ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a phenyl group, or a 4-methylphenyl group; A¹ is a trivalent aromatic group optionally having a substituent; A² and A³ are each independently a divalent aromatic group having 6 to 30 carbon atoms and optionally having a substituent; and Q¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and optionally having a substituent].
 3. The phase difference plate according to claim 1, wherein the polymerizable liquid crystal compound with reverse wavelength dispersion is a compound represented by the following formula (V):

[in the formula Y^(1w) to Y^(8w) are each independently a chemical single bond, —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, wherein R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; G^(1w) and G^(2w) are each independently a divalent linear aliphatic group having 1 to 20 carbon atoms and optionally having a substituent, wherein the linear aliphatic group may have one or more of —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR^(2w)—C(═O)—, —C(═O)—NR^(2w)—, —NR^(2w)—, or —C(═O)— inserted thereinto per one aliphatic group, provided that a case where two or more —O— groups or —S— groups are adjacently inserted is excluded, and wherein R^(2w) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Z^(1w) and Z^(2w) are each independently an alkenyl group having 2 to 10 carbon atoms that may be substituted by a halogen atom; A^(xw) is an organic group of 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; A^(yw) is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 20 carbon atoms and optionally having a substituent, an alkynyl group having 2 to 20 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 12 carbon atoms and optionally having a substituent, —C(═O)—R^(3w), —SO₂—R^(4w), —C(═S)NH—R^(9w), or an organic group of 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, wherein R^(3w) is an alkyl group having 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 20 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 12 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having 5 to 12 carbon atoms, R^(4w) is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group, and R^(9w) is an alkyl group having 1 to 20 carbon atoms and optionally having a substituent, an alkenyl group having 2 to 20 carbon atoms and optionally having a substituent, a cycloalkyl group having 3 to 12 carbon atoms and optionally having a substituent, or an aromatic group having 5 to 20 carbon atoms and optionally having a substituent, wherein the aromatic ring of A^(xw) and A^(yw) may have a substituent, and A^(xw) and A^(yw) may together form a ring; A^(1w) is a trivalent aromatic group optionally having a substituent; A^(2w) and A^(3w) are each independently a divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms and optionally having a substituent; A^(4w) and A^(5w) are each independently a divalent aromatic group having 6 to 30 carbon atoms and optionally having a substituent; and Q^(1w) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms and optionally having a substituent].
 4. The phase difference plate according to claim 2, wherein the polymerizable monomer is a non-liquid crystal compound represented by the following formula (III):

(in the formula (III), Y^(1x) to Y^(6x), G^(1x), G^(2x), Z^(1x), Z^(2x), A^(xx), A^(yx), A^(1x) to A^(3x), and Q^(1x) have the same meanings as Y¹ to Y⁶, G¹, G², Z¹, Z², A^(x), A^(y), A¹ to A³, and Q¹, respectively, in the formula (I), and at least one of them is different from the corresponding group in the co-used compound (I)).
 5. The phase difference plate according to claim 1, wherein the polymerizable monomer has a mesogen, and the mesogen of the polymerizable monomer is oriented in parallel to a main chain mesogen of the polymerizable liquid crystal compound with reverse wavelength dispersion in the optically anisotropic layer.
 6. The phase difference plate according to claim 1, wherein the polymerizable monomer has a mesogen, and the mesogen of the polymerizable monomer is oriented in parallel to a side chain mesogen of the polymerizable liquid crystal compound with reverse wavelength dispersion in the optically anisotropic layer.
 7. The phase difference plate according to claim 1, wherein a ratio of the polymerizable monomer in the composition (A) is 1 to 100 parts by weight relative to 100 parts by weight of the polymerizable liquid crystal compound with reverse wavelength dispersion.
 8. A circularly polarizing plate comprising the phase difference plate according to claim 1 and a linear polarizer.
 9. The circularly polarizing plate according to claim 8, wherein a phase difference of the phase difference plate at a wavelength of 550 nm is 100 to 150 nm, and an angle between a slow axis of the phase difference plate and a transmission axis of the linear polarizer is 45°.
 10. An image display device comprising the phase difference plate according to claim
 1. 